CN102575073B - Glass fibre composite of improved processability - Google Patents
Glass fibre composite of improved processability Download PDFInfo
- Publication number
- CN102575073B CN102575073B CN201080044441.1A CN201080044441A CN102575073B CN 102575073 B CN102575073 B CN 102575073B CN 201080044441 A CN201080044441 A CN 201080044441A CN 102575073 B CN102575073 B CN 102575073B
- Authority
- CN
- China
- Prior art keywords
- mfr
- fiber reinforcement
- propylene
- alfon
- polypropylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Fiber reinforced composition comprising a heterophasic propylene copolymer, a propylene homopolymer and/or a propylene copolymer, and fibers, wherein the propylene copolymer comprises not more than 2.0 wt% C2 to C10 a-olefins other than propylene, the propylene homopolymer and the propylene copolymer have a melt flow rate MFR2 (230 DEG C) of at least 500 g/10 min, and the composition has a melt flow rate MFR2 (230 DEG C) of at least 10 g/10 min.
Description
Technical field
The goods that the present invention relates to a kind of improved fiber-reinforced polypropylene compositions and formed by it.
Background technology
Polypropylene is a kind of material using in numerous technical fields, and enhanced polypropylene has especially obtained related application in the field that depends on uniquely before this non-cohesive material, especially metal.An object lesson of enhanced polypropylene is glass-reinforced polypropylene.These materials can be by selecting polypropylene type, content of glass fiber and the characteristic of design team's compound by the coupling agent type of selecting to use sometimes.Therefore, for need to be compared with for the application of high rigidity, thermal deformation resistant, shock resistance and anti-Dynamic Fracture load property, glass-fiber reinforced polypropylene be now material used for a long time (its example is included in trolley part, the support part for polymer body lath, washing machine and the dishwasher components in engine nacelle with bearing function).Yet a defect of the fiber reinforced material of can business buying is its limited mobility and processing characteristics.Between content of glass fiber (scope is 10-40wt% conventionally) and mobility (MFR), exist this fact of obvious negative correlation to make the formation of thin-walled or slim and frahile parts very difficult or impossible.
Therefore, can not sacrifice mechanical property, especially by changing polymer materials, improve mobility shock strength in the situation that up to now.
EP 1 357 144 B1 described the combination of alfon and heterophasic propylene copolymers or the combination of two kinds of different heterophasic propylene copolymers as matrix for glass fibre reinforcement (fibre content of 5-50wt%).Melt flow rate (MFR) (the MFR of polymeric constituent A (alfon or propylene copolymer)
2) higher than 10g/10min, and the melt flow rate (MFR) (MFR of polymeric constituent B (heterophasic copolymer)
2) be 0.1-2.0g/10min.Overall melt flow rate (MFR) (the MFR of this example
2) be 1.3-6.5g/10min, under higher melt flow rate (MFR), mechanical property is obviously poorer.
EP 0 206 034 A1 have described the polyolefin compositions that comprises fibrous mineral filler (3-25wt%).Matrix for this fibrous packing is alfon or multipolymer and poly composition, the melt flow rate (MFR) (MFR of said composition
2) over 10g/10min, described melt flow rate (MFR) (MFR
2) be 0.1 to 50 times to the melt flow rate (MFR) (MFR of polypropylene component
2).This example is with regard to melt flow rate (MFR) (MFR
2) bulk flow from component, may be estimated as between 1g/10min and 4g/10min.
US 5,382, and 459 disclose glass fiber reinforced polypropylene compositions, and said composition is mainly comprised of heterophasic copolymer, carboxyl acid modified polypropylene (as expanding material) and glass fibre.Its intended application is the injecting wheel tyre surface with higher gloss degree and intensity.Overall melt flow rate (MFR) (MFR
2) and hardness all not by quantitatively.
WO 2008/074715 A1 relates to the polyolefin compositions containing filler, and its polypropylene that comprises 15-55wt% (has melt flow rate (MFR) (MFR
2) surpass respectively 500g/10min and 0.1-30g/10min two components, optionally there is the bimodal mixture of 0.5-15wt% expanding material), the elastomeric polymer of 4-25wt% and the filler of 20-80wt%.Overall melt flow rate (MFR) (the MFR of the example that comprises glass fibre (50wt%)
2) be 3.6-7.8g/10min, the scope of Charpy (Xia Shi shock strength, that is, cantilever beam impact strength) (IS 1791eU ,+23 ℃) is 61-82kJ/m
2, tensile modulus is 9700 to 13100MPa.Yet the mobility of composition still can not be satisfactory.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of fiber reinforcement composition, it has by outstanding mobility in the situation that not sacrificing mechanical property such as modulus in flexure, shock strength and elongation at break.
Discovery of the present invention is, fiber reinforced material must be embedded in the polymer composition that comprises low viscosity polypropylene and heterophasic polypropylene, and described heterophasic polypropylene contains the elastomer copolymer that is no more than 45wt%.
Therefore, the invention reside in a kind of fiber reinforcement composition (the first embodiment) is provided, it comprises:
(a) heterophasic propylene copolymers (HECO),
(b) alfon (H-PP1) and/or propylene copolymer (C-PP1),
(c) fiber (F),
(d) elastomerics (E2) optionally,
And
(e) expanding material (C) optionally,
Wherein,
(i) heterophasic propylene copolymers (HECO) comprises polypropylene-base (M-PP) and is dispersed in the elastomer copolymer (E1) in this matrix, and described elastomer copolymer (E1) comprises the unit that is derived from following substances:
-propylene, and
-ethene and/or C4 to C20 alpha-olefin,
(ii) the cold solubles content of dimethylbenzene (XCS) of measuring according to ISO 6427 (23 ℃) of heterophasic propylene copolymers (HECO) is no more than 45wt%, preferably between 5wt% to 45wt%,
(iii) propylene copolymer (C-PP1) comprises and is no more than C2 to the C10 alpha-olefin of 2.0wt% except propylene, and
(iv) the melt flow rate (MFR) MFR that alfon (H-PP1) and alfon (C-PP1) are measured according to ISO 1133
2(230 ℃) are 500g/10min at least.
Preferably, according to the further feature of the fiber reinforcement composition of the first embodiment, be, compare the melt flow rate (MFR) MFR that polypropylene-base (M-PP) is measured according to ISO 1133 with propylene copolymer (C-PP1) with alfon (H-PP1)
2(230 ℃) are lower.Further, the melt flow rate (MFR) MFR preferably measuring according to ISO 1133 according to the fiber reinforcement composition of the first embodiment
2(230 ℃) are 10g/10min at least.
Alternatively, composition of the present invention (the second embodiment) can be defined as a kind of fiber reinforcement composition, and it comprises:
(a) heterophasic propylene copolymers (HECO),
(b) alfon (H-PP1) and/or propylene copolymer (C-PP1),
(c) fiber (F),
(d) elastomerics (E2) optionally,
And
(e) expanding material (C) optionally,
Wherein,
(i) propylene copolymer (C-PP1) comprises C2 to the C10 alpha-olefin except propylene that is no more than 2.0wt%,
(ii) the melt flow rate (MFR) MFR that alfon (H-PP1) and propylene copolymer (C-PP1) are measured according to ISO 1133
2(230 ℃) are 500g/10min at least, and
(iii) the melt flow rate (MFR) MFR that composition is measured according to ISO 1133
2(230 ℃) are 10g/10min at least.
Preferably, according to the further feature of fiber reinforcement composition of the second embodiment, be, heterophasic propylene copolymers (HECO) comprises polypropylene-base (M-PP) and is dispersed in the elastomer copolymer (E1) in this matrix, and described elastomer copolymer (E1) comprises the unit that is derived from following substances:
-propylene, and
-ethene and/or C4 to C20 alpha-olefin.
More preferably the cold solubles content of dimethylbenzene (XCS) that heterophasic propylene copolymers (HECO) is measured according to ISO 6427 (23 ℃) is no more than 45wt%, preferably within the scope of 5-45wt%.In addition, the melt flow rate (MFR) MFR that optimization polypropylene matrix (M-PP) is measured according to ISO 1133
2(230 ℃) are lower than alfon (H-PP1) and propylene copolymer (C-PP1).
Surprisingly, the present invention finds, by by other characteristics such as rigidity and shock resistance remain in aspiration level, fiber reinforcement composition can have extraordinary mobility.Especially, modulus in flexure, Xia Shi shock strength (that is, cantilever beam impact strength, Charpy impact) and elongation at break meet the requirement that for example automotive industry and appliance industry (referring to table 2 to 4) set.
Embodiment
Now the first embodiment of the present invention and the second embodiment are described in more detail.
From the wording for different polymkeric substance according to the present invention (HECO, M-PP, H-PP1, C-PP1, H-PP2, C-PP2, E1, E2 and C) obviously, they must (chemically) differ from one another.Further aspect of the present invention is the following fact: the polymkeric substance HECO of use (and single component M-PP (H-PP2, C-PP2) and E1), H-PP1, C-PP1 and E2 be not branched chain type.In other words, polymkeric substance HECO (and single component M-PP (H-PP2, C-PP2) and E1), the branch index g ' of H-PP1, C-PP1 and E2 is at least 0.90, is more preferably at least 0.95, such as being 1.00.Branch index g ' is defined as g '=[IV]
br/ [IV]
lin, wherein g ' is branch index, [IV]
brthe limiting viscosity of branched polypropylene, and [IV]
linit is the polyacrylic limiting viscosity of straight chain with weight-average molecular weight identical with branched polypropylene (in ± 10% scope).Therefore, low g ' value is the indication of hyper branched polymer.In other words, if g ' value declines, polyacrylic branching can improve.About this point, please refer to B.H.Zimm and W.H.Stockmeyer, J.Chem.Phys., 17,1301 (1949).By reference this document is incorporated to the application.
Term " heterogeneous " represent elastomer copolymer (E1) and elastomer copolymer (E2) (if any) preferably by (subtly) be at least dispersed in heterophasic propylene copolymers (HECO) polypropylene-base (M-PP) in.In other words, elastomer copolymer (E1) and elastomerics (E2) form inclusion in polypropylene-base (M-PP).Therefore, polypropylene-base (M-PP) contains the not inclusion of (subtly) dispersion of a matrix part, and described inclusion contains respectively elastomer copolymer (E1) and elastomerics (E2).According to term of the present invention " inclusion ", should preferably represent that matrix and inclusion form different phases heterophasic propylene copolymers (HECO) is inner, described inclusion for example by high resolving power microscopy, such as electron microscope technique or scanning pressure microscopy can be seen.Final fiber reinforcement composition may be composite structure.Polypropylene-base (M-PP) may form external phase together with alfon (H-PP1) and/or propylene copolymer (C-PP1), this external phase is the matrix of fiber reinforcement composition, and wherein elastomer copolymer (E1) optionally forms or forms and be dispersed in the inclusion in matrix respectively together with elastomerics (E2).
In addition, the inclusion in final fiber reinforcement composition can also contain fiber (F); Yet optimum fiber (F) is disperseed separately, as the separated inclusion of the final matrix inside at fiber reinforcement composition.
Further, fiber reinforcement composition according to the present invention preferably comprises following substances as at the inner only polymeric constituent of fiber reinforcement composition,, does not have other polymeric constituent that is:
-heterophasic propylene copolymers (HECO),
-alfon (H-PP1) and/or propylene copolymer (C-PP1),
-elastomerics (E2) optionally, and
-expanding material (C) optionally.
Especially when fiber reinforcement composition according to the present invention, take Overall Group's compound as benchmark, preferably take and be present in polymkeric substance in fiber reinforcement composition when benchmark comprises following substances, can obtain good effect:
(a) 5.0-50.0wt%, more preferably 7.0-45.0wt%, the more preferably heterophasic propylene copolymers of 9.0-40wt% (HECO),
(b) 10.0-60.0wt%, more preferably 12.0-55.0wt%, the more preferably mixture of the alfon of 15.0-50.0wt% (H-PP1), propylene copolymer (C-PP1) or alfon (H-PP1) and propylene copolymer (C-PP1)
(c) 10.0-45.0wt%, more preferably 20.0-43.0wt%, the more preferably fiber of 30.0-40.0wt%,
(d) optionally 3.0-20.0wt%, more preferably 5.0-16.0wt%, the more preferably elastomerics of 6.0-13.0wt% (E2), and
(e) optionally 0.5-4.0wt%, more preferably 1.0-3.5wt%, the more preferably expanding material of 1.5-2.5wt% (C).
Further, optimum fiber enhancing composition has quite high melt flow rate (MFR).Melt flow rate (MFR) depends primarily on molecular-weight average.This is owing to the following fact: the short molecule of comparing, longer molecule causes material to have lower flow tendency.The raising of molecular weight means that MFR value reduces.Melt flow rate (MFR) (MFR) be take under specified temperature and pressure condition the polymkeric substance g/10min that disengages by the die orifice limiting and is measured as unit, and for each polymer type, successively, the viscosity measurement of polymkeric substance is mainly subject to the impact of its molecular weight, and is subject to the impact of its degree of branching.At 230 ℃, locate the lower melt flow rate (MFR) of measuring of 2.16kg load (ISO 1133) and be represented as MFR
2(230 ℃).Therefore, preferably in the present invention, the MFR of fiber reinforcement composition
2(230 ℃) are 10g/10min at least, more preferably at least 12g/10min, more preferably 14g/10min at least.On the other hand, final melt flow rate (MFR) MFR
2(230 ℃) should not be too high, to avoid any separation trend of fiber (F).Therefore, the final melt flow rate (MFR) MFR of optimum fiber enhancing composition
2(230 ℃) are in 10 to 100g/10min, preferably 12 to 80g/10min, more preferably 13 to 60g/10min scope.
Further, have been found that, when the cold solubles content of dimethylbenzene (XCS) of heterophasic propylene copolymers (HECO) (measuring according to ISO 6427 (23 ℃) in the present invention) neither too high, low only,, in the time of in 5 to 45wt% scope, can obtain particularly preferred effect.
In addition, preferably (according to ISO 1133, measure) the melt flow rate (MFR) MFR of heterophasic propylene copolymers (HECO)
2(230 ℃) are quite high,, surpass 10g/10min that is, more preferably surpass 20g/10min, more preferably surpass 40g/10min, more preferably surpass 60g/10min, such as surpassing 90g/10min.Therefore, preferably (according to ISO 1133, measure) the melt flow rate (MFR) MFR of heterophasic propylene copolymers (HECO)
2(230 ℃) are in 10.0 to 300.0g/10min scope, more preferably in 30.0 to 200.0g/10min scope, more preferably in 40 to 150g/10min scope.
As mentioned above, heterophasic propylene copolymers (HECO) preferably not only has quite high melt flow rate (MFR) MFR
2(230 ℃), but also there is the cold soluble constituent of quite low dimethylbenzene (XCS).Therefore, particularly preferably heterophasic propylene copolymers (HECO) meets following relational expression:
MFR(HECO)/XCS(HECO)＞4，
Preferred MFR (HECO)/XCS (HECO) > 5,
More preferably MFR (HECO)/XCS (HECO) > 6,
Wherein,
" MFR (HECO) " is according to the MFR of the heterophasic propylene copolymers (HECO) of ISO 1133 measurements
2(230 ℃) [g/10min], and
" XCS (HECO) " is according to the content [wt%] of the cold solvend of dimethylbenzene (XCS) component of the heterophasic propylene copolymers (HECO) of ISO 6427 (23 ℃) measurement.
As mentioned above, heterophasic propylene copolymers (HECO) preferably comprises:
(a) polypropylene-base (M-PP), and
(b) elastomer copolymer that comprises the unit that is derived from following substances (E1):
-propylene, and
-ethene and/or C4 to C20 alpha-olefin.
Further, heterophasic propylene copolymers (HECO) preferably only comprises polypropylene-base (M-PP) and elastomer copolymer (E1) as polymeric constituent.In other words, heterophasic propylene copolymers (HECO) can contain other polymkeric substance as additive, but take overall heterophasic propylene copolymers (HECO) as benchmark, more preferably to take the polymkeric substance being present in heterophasic propylene copolymers (HECO) be benchmark, the content of other polymkeric substance is no more than 5wt%, more preferably no more than 3wt%, such as being no more than 1wt%.The extra polymkeric substance that can exist with low like this content is a polyethylene, and it is the reaction product obtaining by preparing heterophasic propylene copolymers (HECO).Therefore the polyethylene that the heterophasic propylene copolymers (HECO), particularly preferably limiting in the present invention only contains polypropylene-base (M-PP), elastomer copolymer (E1) and optionally exists with the content of addressing in this paragraph.Further, in the present invention, the cold insolubles of dimethylbenzene (XCI) component in heterophasic propylene copolymers (HECO) represents the polyethylene in the heterophasic propylene copolymers (HECO) of polypropylene-base (M-PP) and optional (if present), otherwise the cold solvend of dimethylbenzene (XCS) component represents the elastomer portion in heterophasic polypropylene (H-PP1), that is, elastomer copolymer (E1).
Therefore, as mentioned above, in heterophasic propylene copolymers (HECO), elastomer copolymer (E1) content, that is, the cold solvend of dimethylbenzene (XCS) content is no more than 45wt%, more preferably no more than 40wt%, more preferably no more than 30wt%, more preferably no more than 25wt%.Therefore, preferably at heterophasic propylene copolymers (HECO) Elastic precursor copolymer (E1) content,, the cold solvend of dimethylbenzene (XCS) content preferably 5 to 45wt%, more preferably 7 to 40wt%, more preferably 7 to 35wt%, more preferably 9 to 30wt%, such as 10 to 25wt%.
On the other hand, in heterophasic propylene copolymers (HECO), polypropylene-base (M-PP) content, that is, the cold insolubles of dimethylbenzene (XCI) content, preferably 55wt% at least, more preferably 60wt% at least, more preferably 70wt% at least, more preferably 75wt% at least.Therefore, optimization polypropylene matrix (M-PP) content,, the cold insolubles of dimethylbenzene (XCI) content, preferably in 55 to 95wt% scope, more preferably in 60 to 93wt% scope, more preferably in 65 to 93wt% scope, more preferably in 70 to 91wt% scope, in the scope 75 to 90wt%.As fruit polyethylene is present in heterophasic propylene copolymers (HECO), for the numerical value of polypropylene-base (M-PP) content rather than can be in a slight decrease for the numerical value of the cold insolubles of dimethylbenzene (XCI) content.
Press as mentioned above, heterophasic propylene copolymers (HECO) comprises polypropylene-base (M-PP), is dispersed with elastomer copolymer (E1) in this matrix.
As following explanation, with regard to molecular weight distribution and/or co-monomer content distribution, polypropylene-base (M-PP), alfon (H-PP1) and propylene copolymer (C-PP1) may be single peak type or multimodal, such as bimodal pattern.
Therefore, term " multimodal () as used herein " or " bimodal pattern () " that is refer to the form of polymkeric substance,,
The form of its molecular weight distribution curve, its be molecular weight component with respect to the graphic representation of its molecular weight function,
And/or
The form of its co-monomer content distribution curve, it is that co-monomer content is with respect to the graphic representation of the function of polymeric constituent molecular weight.
As following explanation in detail, if polypropylene-base (M-PP), alfon (H-PP1) and propylene copolymer (C-PP1) be single peak type or multimodal, they can be prepared by the following method: mix different polymer types, that is, the polymkeric substance of different molecular weight and/or co-monomer content.Yet, in this case, preferably by using the reactor with series system structure, and under differential responses condition, operate, in the technique of a consecutive steps, produce polymeric constituent polypropylene-base (M-PP), alfon (H-PP1) and propylene copolymer (C-PP1).Finally, each component of preparing in specific reactor will have its own molecular weight distribution and/or co-monomer content distribution.
When the distribution curve from these components (molecular weight or co-monomer content) thus be applied while obtaining the molecular weight distribution curve of final polymkeric substance or co-monomer content distribution curve, these these curves can demonstrate two above maximum values or at least when comparing with the curve of single component, clearly broaden.That the such polymkeric substance that produce in two above series connection steps are known as bimodal pattern or multimodal, this depends on the quantity of step.
Polypropylene-base (M-PP) may be alfon (H-PP2) or propylene copolymer (C-PP2).
Yet optimization polypropylene matrix (M-PP) is alfon (H-PP2).
The term " alfon " using in the present invention relates to a kind of polypropylene, and it is comprised of propylene units substantially, that is, by surpass 99.5wt%, more preferably at least 99.7wt%, such as the propylene units of 99.8wt% at least forms.In a kind of preferred implementation, in alfon, only propylene units can be detected.The enough FT infrared spectroscopic determinations of co-monomer content energy, as described in the following embodiments.
If polypropylene-base (M-PP) is propylene copolymer (C-PP2), atactic propene copolymer (rC-PP2) more precisely, this propylene copolymer (C-PP2), be that atactic propene copolymer (rC-PP2) also can comprise by the unit that is selected from least one comonomer-derived of lower group except comprising the unit being derived by propylene units: ethene and C4 to C20 alpha-olefin, preferably described at least one comonomer is selected from lower group: ethene and C4 to C10 alpha-olefin, for example 1-butylene or 1-hexene.Propylene copolymer (C-PP2) most preferably, atactic propene copolymer (rC-PP2) is propylene ethylene copolymers or rather.In propylene copolymer (C-PP2), or rather in atactic propene copolymer (rC-PP2), co-monomer content, such as ethylene content is preferably relatively low situation,, 5.0wt% at the most, more preferably 0.5 to 5.0wt%, more preferably 1.0 to 4.5wt%, and more preferably 2.0 to 4.0wt%.Particularly ethene be in propylene copolymer (C-PP2), unique comonomer in atactic propene copolymer (rC-PP2) or rather.
When polypropylene-base (M-PP) is alfon (H-PP2), with regard to molecular weight, alfon (H-PP2) can be multimodal or bimodal pattern.Thereby, when polypropylene-base (M-PP) be propylene copolymer (C-PP2), or rather during atactic propene copolymer (rC-PP2), with regard to co-monomer content and/or molecular weight, described propylene copolymer (C-PP2), atactic propene copolymer (rC-PP2) can be multimodal or rather, such as bimodal pattern.With regard to co-monomer content, particularly preferably propylene copolymer (C-PP2), atactic propene copolymer (rC-PP2) is multimodal or rather, such as bimodal pattern.
Further, when polypropylene-base (M-PP) be multimodal, during such as bimodal pattern, particularly with regard to co-monomer content for multimodal, during such as bimodal pattern, preferred single component exists can affect the content of material behavior.Therefore,, based on polypropylene-base (M-PP), preferably each in these components is at least with the content of 10wt%, to exist.Therefore,, in bimodal pattern system situation, especially, with regard to co-monomer content, the ratio of division of two components (split) is roughly 50: 50.Therefore, in one embodiment, polypropylene-base (M-PP) comprises two components, and their co-monomer content is such as ethylene content is variant, and wherein the amount of first component is that the amount of 40-60wt% and second component is 60-40wt%.
Mode with preferred implementation in next paragraph limits two co-monomer content differences between component.
If polypropylene-base (M-PP) is propylene copolymer (C-PP2), atactic propene copolymer (rC-PP2) or rather, described propylene copolymer (C-PP2), atactic propene copolymer (rC-PP2) comprises at least two components or rather, these two components have different co-monomer content.Preferably propylene copolymer (C-PP2), atactic propene copolymer (rC-PP2) comprises at least two components or rather, more preferably two components, consist of, the co-monomer content of these two components is such as the difference of ethylene content is for 0.8wt% at least, more preferably difference is 1.2wt% at least.On the other hand, in these two components, the difference of co-monomer content should be not too high, that is, and not higher than 6.0wt%, preferably not higher than 5.0wt%, to avoid any separation trend.Therefore, preferably propylene copolymer (C-PP2), atactic propene copolymer (rC-PP2) comprises at least two components or rather, more preferably two components, consist of, the difference of the co-monomer content of these two components is 2.0 to 6.0wt%, more preferably difference is 2.5 to 5.0wt%.Therefore, in one embodiment, propylene copolymer (C-PP2), atactic propene copolymer (rC-PP2) comprises at least two components, preferably two components, consists of or rather, the first component is alfon and second component is propylene copolymer, the co-monomer content of described propylene copolymer, optimal ethylene content are 0.5wt% at least, more preferably 1.5wt% at least, such as 2.0wt% at least, 2.5wt% at least for example.
Can in a polymerization procedure, produce polypropylene-base (M-PP), this step more than one completes in polymerization reactor.The polypropylene-base (M-PP) that preferably comprises two or more different propene polymers can be by for example, in more than two different polymerization reactors (bulk polymerization device and/or Gas-phase reactor; And bulk polymerization device loop reactor preferably) in the polymerization carried out and be produced, in different polymerization reactors, produce whereby and there is the polymkeric substance that different expection molecular weight distribution or monomer form.
Optimization polypropylene matrix (M-PP) is isotactic.Therefore, optimization polypropylene matrix (M-PP) has quite high pentad (pentad) concentration, that is, and and higher than 90mol%, more preferably higher than 92mol%, more preferably higher than 93mol%, more preferably higher than 95mol%, such as higher than 99mol%.
Further, optimization polypropylene matrix (M-PP) has quite high melt flow rate (MFR).Therefore, preferably in the present invention, polypropylene-base (M-PP), that is, the cold insolubles of dimethylbenzene (XCI) component in heterophasic propylene copolymers (HECO), melt flow rate (MFR) MFR
2(230 ℃) are in 80.0 to 500.0g/10min scope, more preferably in 100.0 to 400.0g/10min scope, more preferably in 120.0 to 300.0g/10min scope.
In addition, optimization polypropylene matrix (M-PP) not only has quite high melt flow rate (MFR) MFR
2(230 ℃), and there is the cold soluble constituent of quite low dimethylbenzene (XCS).Therefore, optimization polypropylene matrix (M) meets following relational expression:
MFR/XCS＞30，
Preferred MFR/XCS > 40,
More preferably MFR/XCS > 50,
Wherein,
" MFR " is according to the MFR of the polypropylene-base (M-PP) of ISO 1133 measurements
2(230 ℃) [g/10min], and
" XCS " is the content [wt%] of the cold solvend of dimethylbenzene (XCS) component in the polypropylene-base (M-PP) of measuring according to ISO 6427 (23 ℃).
The cold solvend component of dimethylbenzene (XCS) in the polypropylene-base (M-PP) of preferably measuring according to ISO 6427 (23 ℃) is 1.0wt% at least.More preferably the cold solvend component of dimethylbenzene (XCS) in polypropylene-base (M-PP) is no more than 3.5wt%, is preferably no more than 3.0wt%, such as being no more than 2.6wt%.Therefore, preferred scope is 1.0 to 3.5wt%, and more preferably 1.0 to 3.0wt%, and more preferably 1.2 to 2.6wt%.
Take overall heterophasic propylene copolymers (HECO) as benchmark, more preferably take the content of polymeric constituent in heterophasic propylene copolymers (HECO) as benchmark, more preferably to take the total content of polypropylene-base (M-PP) and elastomer copolymer (E1) be benchmark, preferably in heterophasic propylene copolymers (HECO), the content of propylene is 75 to 95wt%, and more preferably 80 to 94wt%.Remaining part forms comonomer, optimal ethylene.Therefore, in a preferred embodiment, co-monomer content, that is, C2 to the C10 alpha-olefin content except propylene, is 5 to 25wt%, more preferably 6 to 20wt%.
The second component of heterophasic propylene copolymers (HECO) is elastomer copolymer (E1).
Elastomer copolymer (E1) comprises: can by (i) propylene and (ii) ethene and/or at least another kind of C4 to C20 alpha-olefin, such as the alpha-olefin derived unit of C4 to C10; More preferably can be by (i) propylene and (ii) ethene and at least another kind of alpha-olefin derived unit, described another kind of alpha-olefin is selected from lower group: 1-butylene, 1-amylene, 1-hexene, 1-heptene and 1-octene.Preferred elastomeric precursor copolymer (E1) is comprised of said units.Elastomer copolymer (E1) can contain the unit being derived by non-conjugated diene in addition, yet preferred elastomeric precursor copolymer (E1) is only by can be by (i) propylene and (ii) ethene and/or the alpha-olefin derived unit of C4 to C20 form.If you are using, suitable non-conjugated diene comprises: straight chain and side chain acyclic diene, such as 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and the mixed isomers of dihydromyrcene and dihydro ocimene; The alicyclic diene of monocycle, such as 1，4-cyclohexadiene, 1,5-cyclooctadiene, 1,5-encircles 12 diene, 4 vinyl cyclohexene, 1-allyl group-4-isopropylidene hexanaphthene, 3-allyl group cyclopentenes, 4-tetrahydrobenzene and 1-pseudoallyl-4-(4-butenyl) hexanaphthene.Many ring-like alicyclic condensed ring diene and bridged ring diene are also suitable, comprising: tetrahydroindene, methyl tetrahydroindene, Dicyclopentadiene (DCPD), two rings (2,2,1) heptan-2,5-diene, 2-methyl bicyclic heptadiene, and alkenyl norbornylene, alkylidene group norbornylene, cycloalkenyl norbornylene, with ring alkylidene group norbornylene, such as 5-methylene-2-norbornene, 5-isopropylidene norbornylene, 5-(4-cyclopentenyl)-2-norbornylene, and 5-cyclohexylidene-2-norbornylene.Preferred non-conjugated diene is 5-ethylidene-2-norbornene, Isosorbide-5-Nitrae-hexadiene and Dicyclopentadiene (DCPD).
Therefore, elastomer copolymer (E1) at least comprises can be by the unit of propylene and ethylene derivative, and can comprise other alpha-olefin derived unit that can be limited in last paragraph by other.Yet particularly preferably elastomer copolymer (E1) only comprises by propylene and ethene and the non-conjugated diene that optionally limits in last paragraph such as the derivative unit of Isosorbide-5-Nitrae-hexadiene.Therefore, especially optimal ethylene propylene non-conjugated diene monomers polymkeric substance (EPDM1) and/or ethylene-propylene rubber(EPR) (EPR1) is as elastomer copolymer (E1), most preferably ethylene-propylene rubber(EPR) (EPR1).
As polypropylene-base (M-PP), elastomer copolymer (E1) may be single peak type or multimodal, such as bimodal pattern.About single peak type and multimodal, such as the definition of bimodal pattern, can be with reference to content as mentioned above.
In the present invention, in elastomer copolymer (E1), can be equal to by the content of the unit of propylene derived can be in the cold solvend of dimethylbenzene (XCS) component detected propylene content.Therefore, the scope of the propylene that can detect in the cold solvend of dimethylbenzene (XCS) component is 50.0 to 75.0wt%, and more preferably 55.0 to 70.0wt%.Therefore, in a specific embodiment, elastomer copolymer (E1), that is, the cold solvend of dimethylbenzene (XCS) component, comprising 25.0 to 50.0wt%, more preferably 30.0 to 45.0wt% can be by the unit of ethylene derivative.Preferred elastomeric precursor copolymer (E1) is ethylene, propylene non-conjugated diene monomers polymkeric substance (EPDM1) or the ethylene-propylene rubber(EPR) (EPR1) with defined in this paragraph propylene and/or ethylene content, especially preferably ethylene-propylene rubber(EPR) (EPR1).
The present invention further preferred requirement is that in heterophasic propylene copolymers (HECO), the limiting viscosity (IV) of the cold solvend of dimethylbenzene (XCS) component is quite low.Quite high limiting viscosity numerical value can improve the ductility (ductility) of heterogeneous system.Therefore, the limiting viscosity of the middle cold solvend of dimethylbenzene (XCS) component of preferred heterophasic propylene copolymers (HECO) is lower than 3.0dl/g, more preferably less than 2.8dl/g, more preferably less than 2.5dl/g.More preferably in heterophasic propylene copolymers (HECO), the limiting viscosity of the cold solvend of dimethylbenzene (XCS) component is in 1.5 to 3.0dl/g scope, and more preferably, in 1.7 to 2.8dl/g scope, more preferably 1.8 to 2.6dl/g.Limiting viscosity is measured in naphthalane according to ISO 1628 at 135 ℃.
In addition, the melt flow rate (MFR) MFR of preferred heterophasic propylene copolymers and/or polypropylene-base (M-PP)
2(230 ℃) [measuring according to ISO 1133] is lower than the melt flow rate (MFR) MFR of alfon (H-PP1) and propylene copolymer (C-PP1)
2(230 ℃) [measuring according to ISO 1133].
Therefore, the melt flow rate (MFR) MFR of heterophasic propylene copolymers (HECO) particularly preferably
2(230 ℃) compare the melt flow rate (MFR) MFR of alfon (H-PP1) and propylene copolymer (C-PP1)
2[(MFR (HECO)/MFR (H-PP1)) or [(MFR (HECO)/MFR (C-PP1))] is in the scope of 1: 4 to 1: 50, more preferably in the scope of 1: 6 to 1: 40 for the ratio of (230 ℃).The melt flow rate (MFR) MFR of heterogeneous system not only
2(230 ℃) should be different from respectively the melt flow rate (MFR) MFR of alfon (H-PP1) and propylene copolymer (C-PP1) like this
2(230 ℃), but also the preferred melt flow rate (MFR) MFR of the matrix of each heterogeneous system part
2(230 ℃) also should be different from respectively the melt flow rate (MFR) MFR of alfon (H-PP1) and propylene copolymer (C-PP1)
2(230 ℃).As mentioned above, heterophasic propylene copolymers (HECO) can characterize by the cold solvend of dimethylbenzene (XCS) component and the cold insolubles of dimethylbenzene (XCI) component.In this application, the cold insolubles of dimethylbenzene (XCI) component of heterophasic propylene copolymers (HECO) is substantially identical with the matrix of described heterophasic propylene copolymers (HECO).Therefore, during the melt flow rate (MFR) of the polypropylene-base (M-PP) in talking about heterophasic propylene copolymers (HECO), just mean the melt flow rate (MFR) of the cold insolubles of dimethylbenzene (XCI) component in described heterophasic propylene copolymers (HECO).Therefore the melt flow rate (MFR) MFR, measuring according to ISO 1133 with alfon (H-PP1) and propylene copolymer (C-PP1)
2(230 ℃) are compared respectively, the melt flow rate (MFR) MFR that the cold insolubles of dimethylbenzene (XCI) component in heterophasic propylene copolymers (HECO) is measured according to ISO 1133
2(230 ℃) are lower, preferably low at least 250g/10min, more preferably low at least 300g/10min, more preferably low at least 400g/10min.
According to above-mentioned, understand the melt flow rate (MFR) MFR that preferably alfon (H-PP1) and propylene copolymer (C-PP1) are measured according to ISO 1133
2(230 ℃) are 500g/10min at least, more preferably 600g/10min at least, more preferably 700g/10min at least.Therefore the melt flow rate (MFR) MFR that, preferably alfon (H-PP1) and propylene copolymer (C-PP1) are measured according to ISO 1133
2(230 ℃) are respectively in 500 to 2,000g/10min scope, more preferably in 600 to 1,500g/10min scope, such as 700 to 1,300g/10min.
Obtain respectively having the alfon (H-PP1) of such higher melt flow speed and a possibility of propylene copolymer (C-PP1) is viscosity breaking.Therefore, preferably before viscosity breaking, the melt flow rate (MFR) MFR of alfon (H-PP1) and propylene copolymer (C-PP1)
2(230 ℃) are no more than respectively 150g/10min, more preferably in 20 to 120g/10min scope, more preferably in 30 to 100g/10min scope.Initial alfon (H-PP1) or the propylene copolymer (C-PP1) using preferably selected by following this mode: viscosity breaking ratio [final MFR
2(230 ℃)/initial MFR
2(230 ℃)] be 1.3 to 10.0, more preferably 2.0 to 6.5, wherein, " initial MFR
2(230 ℃) " be the melt flow rate (MFR) MFR of alfon before viscosity breaking (H-PP1) or propylene copolymer (C-PP1)
2(230 ℃), and " final MFR
2(230 ℃) " be the melt flow rate (MFR) MFR of alfon (H-PP1) or propylene copolymer (C-PP1) after the viscosity breaking
2(230 ℃).Certainly, the alfon (H-PP1) and the propylene copolymer (C-PP1) that limit in the present invention can not obtain by polymerization in the situation that there is no viscosity breaking yet.Typically, in these polymerization techniques, can use Ziegler-Natta catalyst and/or single-site catalysts.If alfon (H-PP1) and propylene copolymer (C-PP1) should characterize by narrow molecular weight distribution extraly, use homopolymer viscosity breaking or that produce by single-site catalysts (H-PP1) and propylene copolymer (C-PP1).
As mentioned above, when alfon (H-PP1) and propylene copolymer (C-PP1) are during by viscosity breaking, they can further characterize by the molecular weight distribution being rather narrow.The viscosity breaking of polymkeric substance has not only improved melt flow rate (MFR), and makes extraly molecular weight distribution narrow down.Similarly, narrow molecular weight distribution also can obtain in the polymerization that adopts single-site catalysts.Therefore, the molecular weight distribution (M of preferred alfon (H-PP1) and propylene copolymer (C-PP1)
w/ M
n) in 2.0 to 6.0 scope, more preferably in 3.0 to 5.0 scope.
Alfon (H-PP1) is isotactic alfon preferably.Therefore, optimization polypropylene matrix (H-PP1) has quite high pentad concentration, that is, and and higher than 90mol%, more preferably higher than 92mol%, more preferably higher than 93mol%, more preferably higher than 95mol%, such as higher than 99mol%.
The melting temperature (Tm) Tm that preferably alfon (H-PP1) is measured according to ISO 11357-3 is at least 145 ℃, more preferably at least 150 ℃.
Further, alfon (H-PP1) has the cold solvend of quite low dimethylbenzene (XCS) content, that is, and and lower than 4.5wt%, more preferably less than 4.0wt%, more preferably less than 3.7wt%.Therefore, the preferred cold solvend of dimethylbenzene (XCS) content is in 0.5 to 4.5wt% scope, more preferably in 1.0 to 4.0wt% scope, more preferably in 1.5 to 3.7wt% scope, in the scope 2.0 to 3.5wt%.
Propylene copolymer (C-PP1) preferably comprises the unit being derived by following substances, preferably this unit, consists of:
(i) propylene, and
(ii) ethene and/or at least one C4 to C20 alpha-olefin, preferably at least one is selected from the alpha-olefin of lower group: ethene, 1-butylene, 1-amylene, 1-hexene and 1-octene, more preferably ethene and/or 1-butylene, more preferably ethene.
Therefore, propylene copolymer (C-PP1) can comprise by propylene, ethene and at least another kind of C optionally
4to C
10alpha-olefin derived unit.Of the present invention one concrete aspect, propylene copolymer (C-PP1) comprises the unit that is derived from following substances: propylene, ethene and the optionally at least another kind of alpha-olefin that is selected from lower group: C
4alpha-olefin, C
5alpha-olefin, C
6alpha-olefin, C
7alpha-olefin, C
8alpha-olefin, C
9alpha-olefin and C
10alpha-olefin.More preferably propylene copolymer (C-PP1) comprises the unit that is derived from following substances: propylene, ethene and the optionally at least another kind of alpha-olefin that is selected from lower group: 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene, wherein 1-butylene and 1-hexene are preferred.Particularly preferably propylene copolymer (C-PP1) is comprised of the unit of propylene and ethylene derivative.Preferably can be by the major portion of the cell formation propylene copolymer (C-PP1) of propylene derived, at least 95.0wt%, preferably at least 97.0wt%, more preferably at least 98.0wt%, more preferably 95.0 to 99.5wt%, preferred 97.0 to 99.5wt%, more preferably 98.0 to 99.2wt%.In propylene copolymer (C-PP1) by the C except propylene
2to C
20the content of alpha-olefin derived unit in 0.5 to 5.0wt% scope, more preferably in 0.5 to 3.0wt% scope, more preferably in 0.8 to 2.0wt% scope.In propylene copolymer (C-PP1), particularly, when propylene copolymer only comprises can be by the unit of propylene and ethylene derivative time, the content of ethene is in 0.5 to 5.0wt% scope, preferably in 0.8 to 2.0wt% scope.
Further, the cold solvend of dimethylbenzene (XCS) content in preferred propylene copolymer (C-PP1) is quite low.Therefore, the cold solvend of dimethylbenzene (XCS) component that preferably propylene copolymer (C-PP1) is measured according to ISO 6427 (23 ℃) is no more than 14.0wt%, more preferably no more than 13.0wt%, more preferably no more than 12.0wt%, such as being no more than 11.5wt%.Therefore, preferred scope is 1.0 to 14.0wt%, and more preferably 1.0 to 13.0wt%, and more preferably 1.2 to 11.0wt%.
Preferably propylene copolymer (C-PP1) is isotactic.Therefore, preferably propylene copolymer has quite high pentad concentration, that is, and and higher than 95mol%, more preferably higher than 97mol%, more preferably higher than 98mol%.
Further, preferably inner by the C except propylene at propylene copolymer (C-PP1)
2to C
20alpha-olefin derived unit is random distribution.Compare with the comonomer total amount in polymer chain, degree of randomness (randomness) can be indicated the content of separated comonomer unit, that is adjacent does not have the content of the unit of other comonomer.A kind of preferred embodiment in, the degree of randomness of propylene copolymer (C-PP1) is at least 30%, more preferably at least 50%, further preferably at least 60%, more preferably at least 65%.
In addition, the melting temperature (Tm) Tm that preferably propylene copolymer (C-PP1) is measured according to ISO 11357-3 is at least 140 ℃, preferably at least 145 ℃, more preferably at least 150 ℃.Therefore, preferably 140 to 164 ℃ of melting temperature (Tm) scopes, preferred scope are 150 to 160 ℃.
When fiber reinforcement composition comprises elastomerics (E2) in addition, can obtain especially good effect.In this case, preferred elastomer (E2) (chemically) is different from elastomer copolymer (E1).
According to elastomerics of the present invention (E2) preferably polyethylene, particularly LLDPE (LLDPE).Therefore, elastomerics (E2), that is, and the density that LLDPE (LLDPE) is measured according to ISO 1183-187 820 to 905kg/m
3scope in, more preferably 840 to 900kg/m
3scope in, more preferably 850 to 890kg/m
3scope in, such as 860 to 885kg/m
3scope in.
Further, elastomerics (E2), LLDPE (LLDPE) can characterize by specific melt flow rate (MFR), that is, and the melt flow rate (MFR) MFR measuring according to ISO 1133
2(190 ℃) are in 0.5 to 50.0g/10min scope, more preferably in 1.0 to 35.0g/10min scope.
Preferably, elastomerics (E2), LLDPE (LLDPE) be contain can be by the unit of ethylene derivative the multipolymer as major portion.Therefore, preferred elastomer (E2), LLDPE (LLDPE) comprise at least 50.0wt% can by the unit of ethylene derivative, more preferably at least 55.0wt% by the unit of ethylene derivative.Therefore, preferred elastomer (E2), LLDPE (LLDPE) comprise 50.0 to 70.0wt%, more preferably 55.0 to 65wt% can be by the unit of ethylene derivative.The comonomer that is present in elastomerics (E2) and is in LLDPE (LLDPE) is C4 to C20 alpha-olefin, such as 1-butylene, 1-hexene and 1-octene, and especially preferred the latter.Therefore, in a specific embodiment, elastomerics (E2), LLDPE (LLDPE) is ethene-1-octene polymer or ethene-1-hexene oligomerization thing with content given in this paragraph.
The further basal component being present in fiber reinforcement composition is fiber (F).Optimum fiber (F) is selected from lower group: glass fibre, steel fiber, ceramic fiber and graphite fibre.Glass fibre is particularly preferred.This glass fibre may be glass fibre or the long glass fibres prescinding, although preferably use the glass fibre that prescinds, be also called staple fibre or chopped glass tow.In general, glass fibre may have 1 to 50mm length.The glass fibre preferred length that prescind or short using in fiber reinforcement composition is 1.0 to 10.0mm, more preferably 3.0 to 7.0mm, and/or diameter is 8 to 20 μ m, more preferably 10 to 15 μ m.
As mentioned before, fiber reinforcement composition can also comprise expanding material (C).
Expanding material (C) preferably comprises (functionalization) polymkeric substance of modification and optionally has the low-molecular weight compound of reactive polar groups.The alpha-olefinic polymer of modification, particularly alfon and multipolymer, such as ethene and propylene mutually multipolymer each other or the multipolymer of ethene and propylene and other alpha-olefins be most preferred because the polymkeric substance in they and fiber reinforcement composition is highly compatible.Can use modified poly ethylene equally.
With regard to structure, polymer-modified graft copolymer or the segmented copolymer of being preferably selected from.
About this point, the preferred polymer-modified group being derived by polar compound that contains, described polar compound especially can be selected from lower group: acid anhydrides, carboxylic acid, carboxylic acid derivative, primary amine and secondary amine, oxy-compound, oxazoline and epoxy compounds and ionic compound.
The object lesson of described polar compound has undersaturated cyclic acid anhydride and their aliphatic diester and two acid derivatives.Especially, can use maleic anhydride and be selected from the compound of lower group: C
1to C
10the dialkyl group maleic acid ester of straight chain and side chain, C
1to C
10the dialkyl group fumaric acid esters of straight chain and side chain, itaconic anhydride, C
1to C
10the methylene-succinic acid dialkyl of straight chain and side chain, toxilic acid, fumaric acid, methylene-succinic acid and their mixture.
Particularly preferably use and use the propene polymer of maleic anhydride graft as polymer-modified, that is, and expanding material (C).
Can be with simple means, disclosed in for example in EP 0572028, exist under the condition of free-radical generating agent (such as organo-peroxide), for example, by the reactive extrusion of polymkeric substance, carry out reactive extrusion with maleic anhydride, prepare polymer-modified, that is, expanding material (C).
Polymer-modified, in expanding material (C), the preferred content of the group being derived by polar compound is 0.5 to 3wt%.
Polymer-modified, i.e. the melt flow rate (MFR) MFR of expanding material (C)
2the preferred value of (230 ℃) is 1.0 to 500g/10min.
Composition of the present invention can contain extraly typical other for example at the useful additive of automotive field, such as carbon black, other pigment, antioxidant, ultra-violet stabilizer, nucleator, static inhibitor and surface slip agent, its consumption is the common consumption in the art.
All components for the preparation of fiber reinforcement composition of the present invention are all known.Therefore, their goods are also well-known.For example, according to heterophasic polypropylene of the present invention (HECO), preferably in multi-step process known in the art, produce, wherein, at least in a slurry-phase reactor, produce polypropylene-base (M-PP), and at least in a Gas-phase reactor, produce elastomer copolymer (E1) subsequently.
Therefore, this polymerization system may comprise an above conventional stirring-type slurry-phase reactor and/or an above Gas-phase reactor.The reactor preferably using is selected from lower group: loop reactor and Gas-phase reactor, particularly, this technique is used at least one loop reactor and at least one Gas-phase reactor.Also likely with series system, use several all types of reactors, for example a loop reactor and two or three Gas-phase reactor, or two loop reactors and one or two Gas-phase reactor.
Preferably this technique also comprises the prepolymerization of using selected catalyst system, and as hereinafter described in detail, described catalyst system comprises Z-N Primary Catalysts, external donor and promotor.
A kind of preferred embodiment in, according to the bulk slurry polymerization methods in propylene liquid, carry out prepolymerization, that is, liquid phase mainly comprises propylene, simultaneously the content of other reactant is less, and optionally inert component is dissolved in liquid phase.
Typically 0 to 50 ℃, preferably from 10 to 45 ℃, more preferably 15 to 40 ℃ of temperature, carry out prepolymerization.
Pressure in pre-polymerization reactor is not crucial, but must be enough high, to keep reaction mixture to be liquid phase.Therefore, pressure can be 20 to 100 bar, for example 30 to 70 bar.
Preferably catalyst component is all introduced to prepolymerization step.Yet if ingredient of solid catalyst (i) and promotor (ii) charging individually can only be introduced prepolymerization step by a part of promotor, remaining part is introduced into polymerization procedure subsequently.And, in the case, be necessary so many promotors to introduce prepolymerization step, obtain therein sufficient polyreaction.
Other component can also be added to prepolymerization step.Therefore, hydrogen can be added to prepolymerization step, to control the molecular weight of prepolymer according to methods known in the art.In addition, can prevent that particle is adhering to each other or adhere on the wall of reactor with static inhibitor.
The accurate control of prepolymerization condition and reaction parameter is well known to those skilled in the art.
Slurry-phase reactor represents any reactor, such as continuous mixing tank reactor or simple batch type tank reactor or loop reactor, in body or slurry, operates, and polymer formation particulate form therein." body " refers to the polymerization in comprising the reaction medium of 60wt% monomer at least.According to preferred embodiment, slurry-phase reactor comprises body loop reactor.
" Gas-phase reactor " refers to any mechanically mixing reactor or fluidized-bed reactor.Preferably Gas-phase reactor comprises mechanical agitation fluidized-bed reactor, and gas velocity is 0.2m/ at least second.
The especially preferred embodiment for the preparation of heterophasic polypropylene of the present invention (HECO) is included in the technique of combination of the combination that comprises a loop reactor and one or two Gas-phase reactor or two loop reactors and one or two Gas-phase reactor and carries out polymerization.
A preferred multi-step process is slurry-gas phase process, such as company of Borealis develops and is known as
technology.Aspect this, can be with reference to EP 0887379 A1, WO 92/12182, WO 2004/000899, WO2004/111095, WO 99/24478, WO 99/24479 and WO 00/68315.They are introduced to the present invention as a reference.
Another suitable slurry-gas phase process is Basel company (Basell)
technique.
Preferably heterophasic polypropylene composition according to the present invention is by using special Z-N Primary Catalysts to combine and produce with special external donor, as described in detail below, preferably adopts
or
technique.
Therefore a preferred multi-step process can comprise following step:
-in the first slurry-phase reactor and optionally in the second slurry-phase reactor (two slurry-phase reactors use identical polymerizing condition), under the condition existing at the catalyst system of choosing, produce polypropylene-base, for instance, as described in detail below, this catalyst system comprises special Z-N Primary Catalysts (i), external donor (iii) and promotor (ii)
-slurry-phase reactor product is transferred to at least one first Gas-phase reactor, such as the first Gas-phase reactor and second Gas-phase reactor of a Gas-phase reactor or series connection,
-in described at least the first Gas-phase reactor, under the condition of polypropylene-base and catalyst system existence, produce elastomer copolymer,
-reclaim polymer product, for further processing.
With regard to above-mentioned preferred slurry-gas phase process, can provide the following general information about process conditions.
Preferably 40 to 110 ℃ of temperature, preferably between 50 and 100 ℃, especially between 60 and 90 ℃, simultaneously pressure in the scope of 20 to 80 bar, preferred 30 to 60 bar, simultaneously optionally hydrogenation to control in a known manner molecular weight.
Slurry polymerization preferably carries out in loop reactor, then reaction product is transferred to Gas-phase reactor subsequently, therein temperature preferably in the scope of 50 to 130 ℃, more preferably 60 to 100 ℃, pressure in the scope of 5 to 50 bar, preferred 8 to 35 bar, simultaneously optionally hydrogenation to control in a known manner molecular weight.
In reactor segment as above, can change mean residence time.In one embodiment, in slurry-phase reactor, for example loop reactor, mean residence time is in the scope of 0.5 to 5 hour, for example 0.5 to 2 hour, and mean residence time in Gas-phase reactor is generally 1 to 8 hour.
As needs, can in slurry-phase reactor, preferred loop reactor, under super critical condition, carry out in known manner polymerization, and/or as polycondensation pattern, in Gas-phase reactor, carry out polymerization.
According to the present invention, under the condition preferably existing at catalyst system as mentioned above, by multistep polymerization technique, obtain heterophasic polypropylene (HECO), this catalyst system comprises the Z-N Primary Catalysts as component (i), the ester exchange offspring that this catalyzer contains lower alcohol and phthalic ester.
Catalyzer used according to the invention is prepared by following step:
A) make MgCl
2solidify adducts and TiCl with spray crystallization adducts or the emulsion of C1-C2 alcohols
4reaction,
B) described C therein
1-C
2between the phthalic acid dialkyl of alcohols and described general formula (I), can there is transesterify to form under the condition of internal donor, step product a) is reacted with the phthalic acid dialkyl of general formula (I)
R wherein
1' and R
2' be at least one C independently
5alkyl,
C) product washing step b), or
D) optionally make step c) product and extra TiCl
4reaction.
According to the method for example limiting, produce Primary Catalysts in patent application WO 87/07620, WO 92/19653, WO 92/19658 and EP 0491566.At this, by reference the content of these files is incorporated to herein.
First, form MgCl
2and C
1-C
2the adducts of alcohols, its chemical formula is MgCl
2* nROH, wherein, R is methyl or ethyl, n is 1 to 6.Preferably use ethanol as alcohols.
By being first melted and following by spraying crystallization or the curing adducts of emulsion, be used as support of the catalyst.
In next step, making chemical formula spray-crystallised or that emulsion is curing is MgCl
2* the adducts of nROH and TiCl
4contact, thereby form titanizing carrier, wherein, R is methyl or ethyl, preferred ethyl, and n is 1 to 6, then carries out following step:
In described titanizing carrier, add following substances to obtain the first product:
(i) the phthalic acid dialkyl of general formula (I), wherein R
1' and R
2' be at least one C independently
5alkyl, such as at least one C
8alkyl,
Or preferably
(ii) the phthalic acid dialkyl of general formula (I), wherein R
1' and R
2' identical, and be at least one C
5alkyl, such as at least one C
8alkyl,
More preferably
(iii) be selected from the phthalic acid dialkyl of the general formula (I) of lower group: the own ester of phthalic acid third (PrHP), dioctyl phthalate (DOP) (DOP), Di Iso Decyl Phthalate (DIDP) and phthalic acid two (13) ester (DTDP), more preferably the phthalic acid dialkyl of general formula (I) is dioctyl phthalate (DOP) (DOP), such as dimixo-octyl phthalate or phthalic acid two b hexyls, especially phthalic acid two b hexyls
Make described the first product stand suitable transesterification conditions,, temperature higher than 100 ℃, preferably between 100 to 150 ℃, more preferably between 130 to 150 ℃, so that there is transesterify between the described ester group in the phthalic acid dialkyl of described methyl alcohol or ethanol and described general formula (I), thereby form preferably at least 80mol%, more preferably 90mol%, the phthalic acid dialkyl of the general formula of 95mol% (II) most preferably:
R wherein
1and R
2methyl or ethyl, preferred ethyl,
The phthalic acid dialkyl of general formula (II) is internal donor, and
Reclaim described ester exchange offspring as Primary Catalysts composition (component (i)).
A kind of preferred embodiment in, the chemical formula of adducts is MgCl
2* nROH, wherein, R is methyl or ethyl, n is 1 to 6, and this adducts is melted, and then melts is preferably by being injected into by gas in cold solvent or cold gas, adducts is crystallized into form favourable on morphology whereby, described as for example WO 87/07620.The adducts of this crystallization is preferably used as support of the catalyst, and reacts according to the method for describing in WO 92/19658 and WO 92/19653 and useful in the present invention Primary Catalysts.
When removing catalyst residue by extraction, obtain the adducts of titanizing carrier and internal donor, the group wherein being derived by ester alcohol changes.
If retain enough titaniums on carrier, it will be as the active element of Primary Catalysts.
In addition, after above-mentioned processing, repeat titanizing, to guarantee sufficient titanium concentration and the activity of bringing thus.
Preferably Primary Catalysts used according to the invention contains maximum 2.5wt%, preferably 2.2%wt%, the more preferably titanium of 2.0wt% at most at most.Its donor content preferably between 4 to 12wt%, more preferably 6 and 10wt% between.
More preferably by use ethanol as alcohols and use dioctyl phthalate (DOP) (DOP) as the phthalic acid dialkyl of general formula (I), obtain diethyl phthalate (DEP) as internal donor compound, and produce Primary Catalysts used according to the invention.
More preferably catalyzer used according to the invention is that the BHC01P catalyzer of company of Borealis is (according to WO92/19653, according to the preparation of disclosed method in WO 99/24479; Particularly according to WO 92/19658, by means of dioctyl phthalate (DOP), as the phthalic acid dialkyl of general formula (I), prepare) or the commercial catalyst Polytrack 8502 of Grace company.
At another kind of embodiment, Z-N Primary Catalysts can be by being modified vinyl compound generation polymerization under the condition existing at catalyst system, described catalyst system comprises special Z-N Primary Catalysts, external donor and promotor, and the general formula of therein ethylene based compound is:
CH
2＝CH-CHR
3R
4
Wherein, R
3and R
4form together 5 yuan or 6 yuan of saturated, undersaturated or aromatic rings, or the alkyl that representative comprises 1 to 4 carbon atom independently, and modified catalyst is used to preparation according to heterophasic polypropylene composition of the present invention.The vinyl compound of this polymerization can be used as α-nucleator.This modification especially can be used for preparing heterophasic polypropylene (H-PP1).
About the modification of catalyzer, can, with reference to International Application No. WO 99/24478, WO 99/24479 and particularly WO00/68315, as for polyreaction and the reaction conditions that relates to catalyst modification, they be introduced to the present invention as a reference.
In order to produce according to heterophasic polypropylene of the present invention, the catalyst system preferably using also comprises organic metal promoters as component (ii) except special Z-N Primary Catalysts.
Therefore, preferred promoter is selected from lower group: trialkylaluminium, such as triethyl aluminum (TEA), dialkylaluminum chloride, and tri-chlorination aluminum dialkyl.
Component (iii) in the catalyst system using means the external donor into general formula (III):
Si(OCH
3)
2R
2 5(III)
R wherein
5represent the cycloalkyl that there is the branched-chain alkyl of 3～12 carbon atoms, preferably there is the branched-chain alkyl of 3 to 6 carbon atoms or there is the cycloalkyl of 4 to 12 carbon atoms, preferably there are 5 to 8 carbon atoms.
R particularly preferably
5be selected from lower group: sec.-propyl, isobutyl-, isopentyl, the tertiary butyl, tert-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and suberyl.
More preferably external donor is dicyclopentyl dimethoxyl silane [Si (OCH
3)
2(cyclopentyl)
2] or diisopropyl dimethoxy silane [Si (OCH
3)
2(CH (CH
3)
2)
2].
Then additive as above is joined in heterophasic polypropylene, described heterophasic polypropylene is to collect from the end reaction device of series reaction device.Preferably, in a step hybrid technique, before expressing technique or during expressing technique, these additives are mixed in heterophasic polypropylene (HECO).As another kind, select, can prepare masterbatch, wherein first heterophasic polypropylene (HECO) is mixed mutually with some additives only.
By in slurry-phase reactor, for example loop reactor, polymerizing catalyst condition under, make propylene optionally with at least another kind of C
2to C
20alpha-olefin (comonomer) polymerization together, thereby produce respectively at least a portion alfon (H-PP1) or propylene copolymer (C-PP1), can prepare the alfon (H-PP1) and the propylene copolymer (C-PP1) that limit in the present invention respectively.If only a part of alfon (H-PP1) or propylene copolymer (C-PP1) are produced, then this part is transferred to Gas-phase reactor subsequently, wherein in Gas-phase reactor, react with propylene, to produce another part under the condition existing in the first step reaction product.At second step, if needed, other C of charging equally
2to C
20alpha-olefin (comonomer).It is a kind of for forming the part (i) of alfon (H-PP1) or propylene copolymer (C-PP1) and the reactor mixture of part (ii) that this reaction sequence can provide.Certainly, the present invention also may carry out first reaction in Gas-phase reactor, and second polyreaction carried out in slurry-phase reactor, for example loop reactor.In addition, can also put upside down the production sequence of part (i) and part (ii), part (ii) had been pressed and first produced part (i), then produced to described order order is above described.Technique as above at least comprises two polymerization procedures, and it is conducive to provide and can holds manageable reactions steps, can prepare the reactor mixture of expectation.These polymerization procedures can be conditioned, for example, by suitably selecting monomer feed, comonomer feed, hydrogen charging, temperature and pressure to regulate, to suitably regulate the characteristic of the polymerization product obtaining.Especially with regard to comonomer, such as the distribution of ethene, make peace with regard to molecular weight and the MFR during described multi-step polymerization process
2(230 ℃) numerical value, likely obtains multimodal, preferably alfon (H-PP1) or the propylene copolymer (C-PP1) of bimodal pattern.Yet, also can produce respectively alfon (H-PP1) and propylene copolymer (C-PP1) in such as loop reactor at a reactor, a kind of method is preferred.
By using any suitable catalyzer for the preparation of alfon (H-PP1) and propylene copolymer (C-PP1), can carry out respectively the method (reactor or a plurality of reactors of connecting).Preferably by use Ziegler-Natta catalyst, especially high yield Ziegler-Natta catalyst (so-called the 4th generation and the 5th generation type, it is different from the so-called s-generation Ziegler-Natta catalyst of low-yield) carry out method discussed above.The suitable Ziegler-Natta catalyst using in the present invention comprises catalyst component, cocatalyst component and at least one electron donor (internal electron donor and/or external electron-donor, preferably at least one external donor).Preferably, catalyst component is the catalyst component of Ti-Mg system, and typically promotor is Al-alkyl based compound.Suitable catalyzer is especially at US 5,234, and 879, those disclosed in WO92/19653, WO 92/19658 and WO 99/33843.
Preferred external donor is known, and to have silane be donor, such as dicyclopentyl dimethoxyl silane or Cyclohexyl Methyl Dimethoxysilane.
An embodiment for the method for alfon (H-PP1) or propylene copolymer (C-PP1) is ring type phase technique or ring type-gas phase process as discussed above, such as being known as of company of Borealis exploitation
technology, it for example has description in EP 0887379 A1 and WO 92/12182.
With regard to above-mentioned preferred ring type (slurry) phase technique or preferred slurry-gas phase process, can provide the following general information about process conditions.
Temperature is from 40 to 110 ℃, preferably between 60 and 100 ℃, especially between 80 and 90 ℃; Pressure is in the scope of 20 to 80 bar, preferably in the scope of 30 to 60 bar; While is hydrogenation optionally, to control molecular weight.Then, the reaction product of the slurry polymerization preferably carrying out in loop reactor is transferred to (when slurry-gas phase process) in Gas-phase reactor subsequently, therein, temperature preferably within the scope of 50 to 130 ℃, more preferably 80 to 100 ℃, pressure in the scope of 5 to 50 bar, preferred 15 to 35 bar, simultaneously optionally hydrogenation to control molecular weight.
In reactor segment as above, can change the residence time.In embodiment, the residence time in slurry reaction, for example loop reactor is in the scope of 0.5 to 5 hour, for example 0.5 to 2 hour, and residence time in gas-phase reaction be generally 1 to 8 hour.
Can carry out the characteristic of alfon (H-PP1) or the propylene copolymer (C-PP1) of the explained hereafter of above-mentioned approximate for regulation and control by process conditions known to those skilled in the art, for example, by following one or more processing parameters, carry out regulation and control: temperature, hydrogen charging, comonomer feed, propylene feed, catalyzer, external donor type and content, in more than two ratio of division between component of multimodal polymkeric substance.
When respectively alfon (H-PP1) and propylene copolymer (C-PP1) being carried out to viscosity breaking step, viscosity breaking can be carried out in any known mode, such as by using superoxide viscosity breaking reagent to carry out.Typical viscosity breaking reagent is 2, 5-dimethyl-2, 5-bis-(tertiary butyl-peroxide) hexane (DHBP) (for example commercial goods name Luperox101 and Trigonox 101), 2, 5-dimethyl-2, 5-bis-(tertiary butyl-peroxide) hexin-3 (DYBP) (for example commercial goods name Luperox 130 and Trigonox 145), dicumyl-superoxide (DCUP) (for example commercial goods name Luperox DC and Perkadox BC), di-t-butyl-superoxide (DTBP) (for example commercial goods name Trigonox B and Luperox Di), the tertiary butyl-cumyl-superoxide (BCUP) (for example commercial goods name Trigonox T and Luperox 801), and two (t-butyl peroxy-sec.-propyl) benzene (DIPP) (for example commercial goods name Perkadox 14S and Luperox DC).The appropriate level of superoxide used according to the invention is known by those skilled in the art substantially, and the alfon based on viscosity breaking to be stood (H-PP1) and the consumption of propylene copolymer (C-PP1) are, the polyacrylic MFR of viscosity breaking to be stood
2the expectation target MFR of (230 ℃) numerical value and the product that will obtain
2(230 ℃), and can easily calculate respectively.Therefore, the polypropylene content of using of take is benchmark, and the typical amounts of superoxide viscosity breaking reagent is from 0.005 to 0.5wt%, more preferably 0.01 to 0.2wt%.
Typically, according to the present invention, viscosity breaking is in forcing machine, preferably in co-rotating twin screw extruder, carries out, to make under optimum conditions melt flow rate (MFR) be improved.During viscosity breaking, to compare with the molecule compared with lower mol, higher molar amounts initial product molecular chain is interrupted more continually from statistics lecture, as mentioned above, causes the overall decline of molecular-weight average and melt flow rate (MFR) to improve.
By using single-site catalysts, for example metallocene catalyst, can in slurry loop reactor, produce elastomerics (E2), i.e. LLDPE (LLDPE).Suitable metallocene and their preparation method are well-known to those skilled in the art.Can be with reference to EP 0260130, WO 97/28170, WO 98/46616, WO 98/49208, WO99/12981, WO 99/19335, EP 0836608, WO 98/56831, WO 00/34341, EP 0423101 and EP0537130.Particularly preferably by using hafnium metallocene such as two (normal-butyl cyclopentadiene) hafnium dichloride or two (normal-butyl cyclopentadiene) hafnium dibenzyl is prepared elastomerics (E2), i.e. LLDPE (LLDPE).Other possible catalyzer has description in WO 97/28170 and WO 00/40620.
For slurry-phase reactor, temperature of reaction is for example generally, in 60 to 110 ℃ of (85 to 110 ℃) scopes, reactor pressure is for example generally, in 5 to 80 bar (50 to 65 bar) scope, and the residence time is for example generally, in 0.3 to 5 hour (0.5 to 2 hour) scope.The thinner using is generally the aliphatic hydrocarbon of boiling point within the scope of-70 to+100 ℃.In these reactors, as needs, polymerization can be carried out under super critical condition.Preferably, in operate continuously loop reactor, produce polymkeric substance, therein ethylene is aggregated under the condition that polymerizing catalyst and chain-transfer agent exist such as hydrogen as mentioned above.Thinner is inertia aliphatic hydrocarbon typically, preferably Trimethylmethane or propane.Elastomerics (E2) can contain the polymeric additive of various standards such as antioxidant, ultra-violet stabilizer and polymer processing reagent.
For the single component of mixing in fiber reinforcement composition of the present invention, can use conventional mixing or blending device, for example Banbury mixer, two roller rubber mills (2-roll rubber mill), the two-way kneading machine of Bu Shi or twin screw extruder.Preferably mix and complete in co-rotating twin screw extruder.The polymer materials reclaiming from forcing machine is normally pellet form.Then these pellets are preferably further processed, for example, by injection moulding, produce goods and the product of fiber reinforcement composition of the present invention.
According to fiber reinforcement composition of the present invention, can prepare by following method: thereby following material is added to forcing machine and extrude these materials, obtain described fiber reinforcement composition:
(a) heterophasic propylene copolymers (HECO),
(b) mixture of alfon (H-PP1), propylene copolymer (C-PP1) or alfon (H-PP1) and propylene copolymer (C-PP1),
(c) fiber (F),
(d) elastomerics (E2) optionally, and
(e) expanding material (C) optionally.
Fiber reinforcement composition according to the present invention can be made into ball shape and by using any and mixed in well-known and the normally used numerous mixing in mixed with resin field and method for mixing.
The composition of fiber reinforcement composition of the present invention is preferably used to produce moulded product, preferred injection-molded item.Be more preferably for the production of washing machine or dishwasher components and automobile product, particularly automotive interior goods and external articles, such as safety lever, side decorations, ladder retaining frame (step assists), vehicle body lath, turbulence generator (spoiler), dashboard, inner edging etc.
The present invention also provides the goods that comprise polypropene composition of the present invention, such as injection-molded item.Therefore, the present invention particularly can provide washing machine or dishwasher components and the automobile product that comprises polypropene composition of the present invention, particularly automotive interior goods and external articles, such as safety lever, side decorations, ladder retaining frame, vehicle body lath, turbulence generator (spoiler), dashboard, inner edging.
Below will to the present invention, be described in further detail by embodiment.
Embodiment
1. definition/measuring method
The definition of following term and measuring method are applicable to the general description of the invention described above, and embodiment hereinafter, unless otherwise defined.
By
13degree of isotacticity in the quantitative polypropylene of C NMR (Nuclear Magnetic Resonance) spectrum
According to for example document V.Busico and R.Cipullo, Progress in Polymer Science, the method in 2001,26,443-533 is carried out basis and is set, and by quantitative 13C nucleus magnetic resonance (NMR) spectrum, measures degree of isotacticity.Regulate experiment parameter to guarantee the measurement of quantitative spectrum, to be applicable to for example document S.Berger and S.Braun, 200 and More NMR Experiments:A Practical Course 2004, this particular task in Wiley-VCH Weinheim.In a kind of mode known in the art, by using the simple correct ratio of the signal integration of representational position, calculate quantitative values.In pentad level, in the mmmm component that pentad distributes, measure degree of isotacticity.
Number-average molecular weight (M
n), weight-average molecular weight (M
w) and molecular weight distribution (MWD)
By size exclusion chromatography (SEC), use Waters Alliance GPCV 2000 instruments with in-line viscometer, measure.Oven temperature is 140 ℃.Trichlorobenzene is used as solvent (ISO 16014).
Density
According to ISO 1183-187, measure.According to ISO 1872-2:2007, by compression moulding, carry out sample preparation
Melting temperature (Tm) Tm
According to ISO 11357-3, measure
MFR
2(230℃)
According to ISO 1133 (230 ℃, 2.16kg load), measure.
MFR
2(190℃)
According to ISO 1133 (190 ℃, 2.16kg load), measure.
By fourier transform infrared spectroscopy, carry out quantitative co-monomer content
After proofreading and correct basis setting in the well-known mode of a kind of the art via quantitative 13C nucleus magnetic resonance (NMR) spectrum, by quantitative Fourier transform infrared spectroscopy (FTIR), measure co-monomer content.Film is depressed into thickness between 100-500 μ m, and with type of transmission spectra re-recorded.
Specifically, use at 720-722cm
-1and 730-733cm
-1the peak area of the baseline correction of the quantitative band that place observes, measures the ethylene content in polypropylene copolymerization of ethylene multipolymer.Based on reference thin film thickness, obtained quantitative result.
Limiting viscosity
According to the DIN ISO 1628/1 in October, 1999 (in naphthane at 135 ℃), measure.
Tensile modulus; Elongation at break; Yielding stress
According to ISO 527-2 (pinblock speed=50mm/ minute; 23 ℃), use the injected sample (dog bone shape, 4mm is thick) that meets EN ISO 1873-2 to measure.
Modulus in flexure:
In the 80x 10x 4mm injected sample of preparing according to ISO 294-1:1996, according to measuring modulus in flexure in 3 of ISO 178 bendings.
Charpy impact test (Charpy impact test):
According to ISO 1792C/DIN 53453 at 23 ℃ and-20 ℃, by using the 80x 10x 4mm preparing according to ISO 294-1:1996
3injection moulding rod sample, measures the summer than (breach) shock strength (Charpy NIS/IS).
The cold solvend of dimethylbenzene (XCS, wt%)
According to ISO 6427, at 23 ℃, measure the content of xylene soluble part (XCS).
2. embodiment
The preparation of PP2
Catalyzer
According to the method for describing in the embodiment 1 at EP 1741725 A1, prepare metallocene catalyst, for the preparation of alfon PP2.
Polymerization
Borstar PP pilot plant as described below method produce alfon PP2: catalyzer is fed into stirring tank pre-polymerization reactor with the triethyl aluminum as promotor together with 911 Al/Zr ratio [mol/mol], the ratio of reactor inner propene and hydrogen is 0.12mol/kmol propylene, at 25 ℃, operate reactor, mean residence time is 0.3 hour.In loop reactor, under 65 ℃ of temperature and 5500kPa pressure, carry out the first polymerization procedure, with 160kg/h flow, add extra propylene with the ratio of 0.38mol/kmol propylene together with hydrogen, keeping mean residence time is 0.45 hour.The polymkeric substance obtaining is transferred in reactor subsequently, without the particular separation with process gas.In Gas-phase reactor, under 85 ℃ of temperature and 2400kPa pressure, carry out the second polymerization procedure, the ratio with 5.5mol/kmol propylene together with hydrogen is further added respectively propylene.At catalyzer, use after steam passivation, and the polymer powder obtaining with warm nitrogen drying, the homopolymer polypropylene obtaining is mixed together with 0.07wt% calcium stearate and 0.60%Irganox B225 (compound antioxidant is provided by Ciba Specialty Chemicals company) in 230 to 250 ℃ in twin screw extruder.
The MFR of the alfon obtaining
2(2.16kg, 230 ℃) are 1,060g/10min, and density is 902kg/m
3, fusing point is 152 ℃, XS content is 1.0wt%.GPC measurement result is: weight-average molecular weight (M
w) 61kg/mol, number-average molecular weight (M
n) 25kg/mol, molecular weight distribution (M
w/ M
n) 2.4.
Table 1: the heterophasic polypropylene of use (HECO)
| HECO 1 | HECO 2 | ||
| MFR | [g/10min] | 100.0 | 12.0 |
| The MFR of XCI | [g/10min] | 160 | 35.0 |
| XCS | [wt％] | 15 | 29.8 |
| C2 total amount | [wt％] | 8.0 | 15.8 |
| The C2 of XCS | [wt％] | 39 | 45 |
| The IV of XCS | [dl/g] | 1.9 | 1.9 |
" HECO 1 " is the commodity BJ356MO of company of Borealis
" HECO 2 " are the commodity EE041AE of company of Borealis
Table 2: the embodiment of the present invention
| E 1 | E 2 | E 3 | E 4 | ||
| HECO 1 | [wt％] | 32.9 | 26.1 | 31.1 | 33.4 |
| PP 1 | [wt％] | _ | _ | _ | _ |
| PP 2 | [wt％] | 18.2 | 25.0 | 16.0 | 17.7 |
| C 1 | [wt％] | 2.0 | 2.0 | 2.0 | _ |
| C 2 | [wt％] | _ | _ | _ | 2.0 |
| E 1 | [wt％] | 8.0 | - | _ | _ |
| E 2 | [wt％] | 8.0 | 12.0 | 8.0 | |
| E 3 | [wt％] | _ | _ | _ | |
| Glass fibre | [wt％] | 38.0 | 38.0 | 38.0 | 38.0 |
| Total additive | [wt％] | 0.9 | 0.9 | 0.9 | 0.9 |
| MFR 230℃/2.16kg | [g/10min] | 14.6 | 35 | 27 | 29 |
| Tensile modulus | [MPa] | 7798 | 7788 | 7171 | 7618 |
| Tensile strength | [MPa] | 100 | 101 | 88 | 96 |
| Elongation at break | [％] | 3.8 | 3,5 | 4,2 | 3,9 |
| Charpy ISO 179 | |||||
| 1eU+23℃ | [kJ/m 2] | 66 | 68 | 73 | 65 |
| 1eA+23℃ | [kJ/m 2] | 15.9 | 15.3 | 18.6 | 15.5 |
| 1eU-20℃ | [kJ/m 2] | n.d * | n.d * | n.d * | 64 |
*n.d: undetermined
Table 3: the embodiment of the present invention
| E 5 | E 6 | E 7 | E 8 | ||
| HECO 1 | [wt％] | 31.1 | 18.6 | 9.6 | 18.6 |
| PP 1 | [wt％] | _ | - | 49.5 | 40.5 |
| PP 2 | [wt％] | 16.0 | 40.5 | _ | _ |
| C 1 | [wt％] | 2.0 | 2.0 | 2.0 | 2.0 |
| C 2 | [wt％] | _ | _ | ||
| E 1 | [wt％] | _ | _ | _ | _ |
| E 2 | [wt％] | _ | _ | _ | _ |
| E 3 | [wt％] | 12.0 | _ | _ | _ |
| Glass fibre | [wt％] | 38.0 | 38.0 | 38.0 | 38.0 |
| Total additive | [wt％] | 0.9 | 2.00.9 | 0.9 | 0.9 |
| MFR 230℃/2.16kg | [g/10min] | 26 | 75 | 23 | 18 |
| Tensile modulus | [MPa] | 7094 | 8600 | 8891 | 8941 |
| Tensile strength | [MPa] | 85 | 120 | 125 | 125 |
| Elongation at break | [％] | 4.5 | 2.5 | 2.3 | 2.4 |
| Charpy ISO 179 | |||||
| 1eU+23℃ | [kJ/m 2] | 76 | 59 | 50 | 53 |
| 1eA+23℃ | [kJ/m 2] | 20.2 | 11.5 | 12.6 | 12.7 |
| 1eU-20℃ | [kJ/m 2] | 70 | n.d * | n.d * | n.d * |
*n.d: undetermined
Table 4: comparative example
| CE 1 | CE 2 | CE 3 | CE4 | ||
| HECO 1 | [wt％] | 54.1 | 25.8 | 22.8 | 0.0 |
| HECO 2 | [wt％] | 0.0 | 33.3 | 36.3 | 0.0 |
| PP 1 | [wt％] | 0.0 | 0.0 | 0.0 | 59.1 |
| C 1 | [wt％] | 2.0 | 2.0 | 2.0 | 2.0 |
| E 1 | [wt％] | 5.0 | 0.0 | 0.0 | 0.0 |
| Glass fibre | [wt％] | 38 | 38 | 38 | 38 |
| Total additive | [wt％] | 0.9 | 0.9 | 0.9 | 0.9 |
| MFR 230℃/2.16kg | [g/10min] | 7.5 | 3.4 | 5.6 | 31 |
| Tensile modulus | [MPa] | 7878 | 7572 | 7687 | 8702 |
| Tensile strength | [MPa] | 96 | 90 | 84 | 126 |
| Elongation at break | [％] | 3.6 | 3.8 | 4.7 | 1.3 |
| Charpy ISO 179 | |||||
| 1eU+23℃ | [kJ/m 2] | 62 | 65 | 64 | 49 |
| 1eA+23℃ | [kJ/m 2] | 15.7 | 20 | 18.8 | 12.6 |
| 1eU-20℃ | [kJ/m 2] | 62 | n.d * | n.d * | 35 |
*n.d: undetermined
PP 1 is the commodity alfon product HL512FBb of company of Borealis, MFR
2(230 ℃) are 1,200g/10min; XCS is 2.8wt%, and Tm is 158 ℃, molecular weight distribution (M
w/ M
n) be 2.8
PP 2 is according to below describing the experimental alfon of preparation, MFR
2(230 ℃) are 1,060g/10min, and XCS is that 1.0wt%, Tm are 152 ℃, molecular weight distribution (M
w/ M
n) be 2.4
C 1 is the polypropylene Exxelor PO1020 of the commercial maleic anhydride functionalization of Exxon Mobil company, and density is 0.9g/cm
3, MFR (230 ℃/2.16kg) is 430g/10min, MAH content is 1.0mol%
C 2 is polypropylene Scona TPPP 2112FA of the commercial maleic anhydride functionalization of German Kometra company limited, and density is 0.9g/cm
3, MFR (230 ℃/2.16kg) is 5g/10min, MAH content is 1.2mol%.
The E 1 commercial ethylene-octene copolymer ENGAGE 8100 of ShiDow Elastomers company, MFR
2(190 ℃) are 1.0g/10min, and density is 0.87g/cm
3
E 2 is the commercial ethylene-octene copolymer Exact 8230 of Exxon Mobil company, MFR
2(190 ℃) are 1.0g/10min, and density is 0.88g/cm
3.
The E 3 commercial ethylene-octene copolymer ENGAGE 8400 of ShiDow Elastomers company, MFR
2(190 ℃) are 30.0g/10min, and density is 0.87g/cm
3.
Glass fibre is the commodity Vetrotex EC13P968 of Germany Saint-Gobain Vetrotex International company, and it is the glass fibre prescinding, Fibre diameter 13 μ m, and length 6mm, there is coating on surface
Total additive: list in table 2, all compositions in 3 and 4 all contain identical following additives combination: the calcium stearate of 0.1wt% (Calcium stearate SP, purchased from Faci, Italy), three (2 of 0.2wt%, 4-di-tert-butyl-phenyl) (Irgafos 168 for phosphoric acid ester, purchased from CIBA Specialty Chemicals, Switzerland), 1 of 0.2wt%, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-t-butyl-4-hydroxyphenyl) (irganox 1330 for benzene, purchased from CIBA Specialty Chemicals, Switzerland) and two octadecyl-disulphide (Hostanox SE10 of 0.4wt%, purchased from Clariant, Germany).
Claims (15)
1. fiber reinforcement composition, take total composition as benchmark, and it comprises:
(a) the heterophasic propylene copolymers HECO of 5.0-50.0wt%, the cold solubles content XCS of dimethylbenzene that described heterophasic propylene copolymers HECO measures at 23 ℃ according to ISO6427 is 5-45wt%, described heterophasic propylene copolymers HECO comprises polypropylene-base M-PP, is dispersed with the elastomer copolymer E1 that comprises the unit that is derived from following substances in described polypropylene-base M-PP:
-propylene, and
-ethene and/or C4 to C20 alpha-olefin
(b) the alfon H-PP1 of 10.0-60.0wt% and/or propylene copolymer C-PP1, and
(c) the fiber F of 10.0-45.0wt%,
Wherein,
(i) propylene copolymer C-PP1 comprises C2 to the C10 alpha-olefin except propylene that is no more than 2.0wt%,
(ii) the melt flow rate (MFR) MFR that alfon H-PP1 and propylene copolymer C-PP1 measure at 230 ℃ according to ISO1133
2for 600g/10min at least, and
(iii) the melt flow rate (MFR) MFR that described composition is measured at 230 ℃ according to ISO1133
2for 10g/10min at least.
2. fiber reinforcement composition according to claim 1, is characterized in that, described polypropylene-base M-PP is alfon H-PP2.
3. fiber reinforcement composition according to claim 1 and 2, is characterized in that, compares the melt flow rate (MFR) MFR that described polypropylene-base M-PP measures at 230 ℃ according to ISO1133 with alfon H-PP1 with propylene copolymer C-PP1
2lower.
4. fiber reinforcement composition according to claim 1 and 2, is characterized in that, described composition also comprises:
(a) be different from the elastomerics E2 of described elastomer copolymer E1, and/or
(b) expanding material C.
5. fiber reinforcement composition according to claim 4, is characterized in that, take total composition as benchmark, comprises:
(a) 3.0 to 20.0wt% elastomerics E2, and/or
(b) 0.5 to 4.0wt% expanding material C.
6. fiber reinforcement composition according to claim 1 and 2, is characterized in that, described heterophasic propylene copolymers HECO
(a) the melt flow rate (MFR) MFR measuring at 230 ℃ according to ISO1133
2surpass 10g/10min,
And/or
(b) the total C except propylene
2to C
10alpha-olefin content is 5 to 25wt%.
7. fiber reinforcement composition according to claim 1 and 2, is characterized in that, described alfon H-PP1
(a) the melt flow rate (MFR) MFR measuring at 230 ℃ according to ISO1133
2in 600 to 2,000g/10min scope,
And/or
(b) there is molecular weight distribution M
w/ M
nbe 2.0 to 6.0, and/or
(c) the melting temperature (Tm) Tm measuring according to ISO11357-3 is at least 145 ℃.
8. fiber reinforcement composition according to claim 1 and 2, is characterized in that, described propylene copolymer C-PP1
(a) the melt flow rate (MFR) MFR2 measuring at 230 ℃ according to ISO1133 in 600 to 2,000g/10min scope,
And/or
(b) there is molecular weight distribution M
w/ M
nbe 2.0 to 6.0,
And/or
(c) the melting temperature (Tm) Tm measuring according to ISO11357-3 is at least 140 ℃.
9. fiber reinforcement composition according to claim 1 and 2, is characterized in that, described fiber F is selected from lower group: glass fibre, wire, ceramic fiber and graphite fibre.
10. fiber reinforcement composition according to claim 4, is characterized in that, described elastomerics E2 is LLDPE LLDPE.
11. fiber reinforcement compositions according to claim 4, is characterized in that, described elastomerics E2
(a) comprise the unit that is derived from following substances:
-ethene, and
-at least one C
4to C
20alpha-olefin,
And/or
(b) there is ethylene content for 50wt% at least,
And/or
(c) density of measuring according to ISO1183-187 820 to 900kg/m
3scope in,
And/or
(d) the melt flow rate (MFR) MFR measuring at 190 ℃ according to ISO1133
2in 0.5 to 50.0g/10min scope.
12. fiber reinforcement compositions according to claim 4, is characterized in that, described expanding material C is the polypropylene of maleic anhydride functionalization.
13. comprise according to the automobile product of the fiber reinforcement composition described in any one in front claim.
14. bases fiber reinforcement composition described in any one in front claim 1 to 12 is used for the purposes of automobile product.
15. for the preparation of according to the methods of the fiber reinforcement composition described in any one in front claim 1 to 12, thereby it comprises following substances is added to extrusion machine and extrudes the step that these materials obtain described fiber reinforcement composition:
(a) heterophasic propylene copolymers HECO,
(b) mixture of alfon H-PP1 or propylene copolymer C-PP1 or alfon H-PP1 and propylene copolymer C-PP1,
(c) fiber F,
(d) optional elastomerics E2, and
(e) optional expanding material C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09172622A EP2308923B1 (en) | 2009-10-09 | 2009-10-09 | Glass fibre composite of improved processability |
| EP09172622.4 | 2009-10-09 | ||
| PCT/EP2010/064640 WO2011042364A1 (en) | 2009-10-09 | 2010-10-01 | Glass fibre composite of improved processability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102575073A CN102575073A (en) | 2012-07-11 |
| CN102575073B true CN102575073B (en) | 2014-03-19 |
Family
ID=41698165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080044441.1A Expired - Fee Related CN102575073B (en) | 2009-10-09 | 2010-10-01 | Glass fibre composite of improved processability |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US9382410B2 (en) |
| EP (1) | EP2308923B1 (en) |
| KR (1) | KR101411691B1 (en) |
| CN (1) | CN102575073B (en) |
| AU (1) | AU2010305546B2 (en) |
| BR (1) | BR112012007696B1 (en) |
| ES (1) | ES2385459T3 (en) |
| PL (1) | PL2308923T3 (en) |
| SI (1) | SI2308923T1 (en) |
| WO (1) | WO2011042364A1 (en) |
Families Citing this family (61)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2915846B1 (en) * | 2011-07-15 | 2016-09-07 | Borealis AG | High flow polyolefin composition with low shrinkage and clte |
| EP3181637B1 (en) * | 2011-09-21 | 2017-11-29 | Borealis AG | Moulding composition |
| EP2589623A1 (en) | 2011-11-02 | 2013-05-08 | Basell Poliolefine Italia S.r.l. | Polypropylene composition for foaming |
| RU2588568C2 (en) | 2012-04-04 | 2016-07-10 | Бореалис Аг | Polypropylene composition, reinforced by fibers with high fluidity |
| CN103589053B (en) * | 2012-08-14 | 2017-07-11 | 合肥杰事杰新材料股份有限公司 | A kind of long glass fiber-reinforced polypropylene materials, preparation method and applications |
| PL2888321T3 (en) * | 2012-08-27 | 2017-05-31 | Borealis Ag | Polypropylene composite |
| RU2648675C2 (en) * | 2013-05-22 | 2018-03-28 | Бореалис Аг | Polypropylene for film application |
| EP2821434A1 (en) | 2013-07-05 | 2015-01-07 | Basell Poliolefine Italia S.r.l. | Polypropylene compositions containing glass fiber fillers |
| WO2015022127A1 (en) | 2013-08-14 | 2015-02-19 | Borealis Ag | Propylene composition with improved impact resistance at low temperature |
| MX2016001930A (en) | 2013-08-21 | 2016-05-26 | Borealis Ag | High flow polyolefin composition with high stiffness and toughness. |
| US9890275B2 (en) | 2013-08-21 | 2018-02-13 | Borealis Ag | High flow polyolefin composition with high stiffness and toughness |
| WO2015028955A1 (en) * | 2013-08-28 | 2015-03-05 | Sabic Global Technologies B.V. | Soft touch compositions and articles thereof |
| PT2853563T (en) | 2013-09-27 | 2016-07-14 | Borealis Ag | Films suitable for bopp processing from polymers with high xs and high tm |
| KR101459951B1 (en) | 2013-09-27 | 2014-11-07 | 현대자동차주식회사 | Compositions of polypropylene having excellent tectility and scratch resistance |
| EP2860031B1 (en) | 2013-10-11 | 2016-03-30 | Borealis AG | Machine direction oriented film for labels |
| EP3060589B9 (en) | 2013-10-24 | 2018-04-18 | Borealis AG | Low melting pp homopolymer with high content of regioerrors and high molecular weight |
| US9751962B2 (en) | 2013-11-22 | 2017-09-05 | Borealis Ag | Low emission propylene homopolymer with high melt flow |
| CN105793298B (en) | 2013-12-04 | 2019-06-28 | 博里利斯股份公司 | The PP homopolymer without phthalic acid ester for meltblown fibers |
| KR101873134B1 (en) | 2013-12-18 | 2018-06-29 | 보레알리스 아게 | Bopp film with improved stiffness/toughness balance |
| US10696829B2 (en) | 2013-12-20 | 2020-06-30 | Saudi Basic Industries Corporation | Heterophasic propylene copolymer |
| US10227427B2 (en) | 2014-01-17 | 2019-03-12 | Borealis Ag | Process for preparing propylene/1-butene copolymers |
| ES2827285T3 (en) | 2014-02-06 | 2021-05-20 | Borealis Ag | Soft copolymers with high impact resistance |
| ES2767498T3 (en) | 2014-02-06 | 2020-06-17 | Borealis Ag | Transparent and smooth impact copolymers |
| EP2907841A1 (en) | 2014-02-14 | 2015-08-19 | Borealis AG | Polypropylene composite |
| ES2659731T3 (en) | 2014-05-20 | 2018-03-19 | Borealis Ag | Polypropylene composition for automotive interior applications |
| CN106604960B (en) * | 2014-09-05 | 2020-12-29 | 埃克森美孚化学专利公司 | Polymer compositions and nonwoven materials made therefrom |
| ES2676310T3 (en) | 2015-07-01 | 2018-07-18 | Borealis Ag | Composition of fiber reinforced polypropylene with high breaking deformation |
| US10342407B2 (en) * | 2015-07-15 | 2019-07-09 | Whirlpool Corporation | Door assembly for a dishwasher |
| ES2663149T3 (en) * | 2015-11-04 | 2018-04-11 | Borealis Ag | Polypropylene-polyethylene composition with improved fluidity |
| ES2792861T3 (en) * | 2016-01-29 | 2020-11-12 | Borealis Ag | Polyolefin composition with improved toughness |
| DE102016212589A1 (en) * | 2016-07-11 | 2018-01-11 | Röchling Automotive SE & Co. KG | Dimensionally stable composite material with a layer of fiber-reinforced recycled material |
| ES2805977T3 (en) * | 2016-08-03 | 2021-02-16 | Borealis Ag | Fiber-reinforced polypropylene composite material |
| WO2018031731A1 (en) | 2016-08-12 | 2018-02-15 | Dow Global Technologies Llc | Compositions comprising carbon fibers and at least one thermoplastic polyolefin elastomer |
| JP2019524961A (en) | 2016-08-12 | 2019-09-05 | ダウ グローバル テクノロジーズ エルエルシー | Propylene-based composition comprising carbon fiber and thermoplastic polyolefin elastomer |
| EP3309211B1 (en) * | 2016-10-17 | 2018-12-12 | Borealis AG | Fiber reinforced polypropylene composite |
| CN108003423A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of polypropylene toughening additive |
| EP3333221B1 (en) * | 2016-12-09 | 2021-03-17 | Borealis AG | Polypropylene composition for foaming applications |
| US11608432B2 (en) * | 2016-12-12 | 2023-03-21 | Sabic Global Technologies B.V. | Pellet comprising thermoplastic polymer sheath surrounding glass filaments having reduced emissions |
| JP7023602B2 (en) * | 2016-12-27 | 2022-02-22 | サンアロマー株式会社 | Polypropylene resin compound |
| BR112019024854A2 (en) * | 2017-06-13 | 2020-06-09 | Basell Poliolefine Italia Srl | polyolefin composition with reduced odor and haze |
| EP3461860A1 (en) * | 2017-09-29 | 2019-04-03 | Borealis AG | Reinforced polypropylene composition |
| CN111278908A (en) * | 2017-11-13 | 2020-06-12 | 巴塞尔聚烯烃意大利有限公司 | Composition obtained from recycled polyolefins |
| US10619037B2 (en) | 2017-11-21 | 2020-04-14 | Johns Manville | Roofing compositions comprising linear low density polyethylene |
| KR102326791B1 (en) * | 2017-11-27 | 2021-11-16 | 주식회사 엘지화학 | Polypropylene and method for preparing the same |
| EP3495422B1 (en) | 2017-12-05 | 2020-11-11 | Borealis AG | Fiber reinforced polypropylene composition |
| ES2874060T3 (en) | 2017-12-05 | 2021-11-04 | Borealis Ag | Article comprising a fiber-reinforced polypropylene composition |
| ES2864224T3 (en) | 2017-12-05 | 2021-10-13 | Borealis Ag | Fiber-reinforced polypropylene composition |
| EP3502166A1 (en) * | 2017-12-22 | 2019-06-26 | SABIC Global Technologies B.V. | Polypropylene composition comprising glass fibers |
| CN108276679A (en) * | 2018-03-06 | 2018-07-13 | 青岛铭威塑业有限公司 | Toughening type PP plastic barrels and preparation method thereof |
| WO2019215125A1 (en) * | 2018-05-09 | 2019-11-14 | Borealis Ag | Polypropylene-ultrahigh-molecular-weight-polyethylene composition |
| EP3804119A2 (en) | 2018-05-28 | 2021-04-14 | Borealis AG | Devices for a photovoltaic (pv) module |
| KR102388031B1 (en) * | 2018-11-06 | 2022-04-19 | 주식회사 엘지화학 | Polypropylene resin pellet and method for preparing the same |
| WO2020169402A1 (en) * | 2019-02-18 | 2020-08-27 | Sabic Global Technologies B.V. | Composition comprising heterophasic propylene copolymer |
| EP4038136A1 (en) * | 2019-10-01 | 2022-08-10 | Basell Polyolefine GmbH | Propylene based filament for 3d printer |
| US20230183431A1 (en) * | 2020-05-22 | 2023-06-15 | Borealis Ag | Glass fiber composite |
| EP3913005A1 (en) * | 2020-05-22 | 2021-11-24 | Borealis AG | Glass fiber reinforced composite with narrow mwd polypropylene |
| KR20230091124A (en) * | 2020-10-19 | 2023-06-22 | 보레알리스 아게 | Polyolefin composition comprising polypropylene homopolymer and recycled plastic material |
| EP4119611A1 (en) * | 2021-07-13 | 2023-01-18 | Borealis AG | Polyolefin composition comprising polypropylene homopolymer and recycled plastic material |
| EP4141067A1 (en) * | 2021-08-23 | 2023-03-01 | Borealis AG | High melt flow polypropylene composition |
| EP4286476A1 (en) * | 2022-05-31 | 2023-12-06 | Borealis AG | Glass fiber composite |
| CN117683298A (en) * | 2023-12-26 | 2024-03-12 | 青岛中新华美塑料有限公司 | Antibacterial PP material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435313A (en) * | 2002-01-30 | 2003-08-13 | 玛志达株式会社 | Glass filament reinforced resin material for shaping, resin shaped article shaping method and said resin shaped article |
Family Cites Families (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61281144A (en) | 1985-06-06 | 1986-12-11 | Idemitsu Petrochem Co Ltd | Polyolefin resin composition |
| FI80055C (en) | 1986-06-09 | 1990-04-10 | Neste Oy | Process for preparing catalytic components for polymerization of olefins |
| US5077255A (en) | 1986-09-09 | 1991-12-31 | Exxon Chemical Patents Inc. | New supported polymerization catalyst |
| US4997875A (en) | 1988-06-13 | 1991-03-05 | Himont Incorporated | High-melt-flow fiber-reinforced propylene polymer compositions |
| US5036034A (en) | 1989-10-10 | 1991-07-30 | Fina Technology, Inc. | Catalyst for producing hemiisotactic polypropylene |
| US5382459A (en) | 1989-10-20 | 1995-01-17 | Toyoda Gosei Co., Ltd. | Glass fiber reinforced resin composition and wheel cap formed of same |
| US5234879A (en) | 1990-12-19 | 1993-08-10 | Neste Oy | Method for the modification of catalysts intended for the polymerization of olefins |
| FI86866C (en) | 1990-12-19 | 1992-10-26 | Neste Oy | FOERFARANDE FOER MODIFIERING AV CATALYSTATOR AVSEDDA FOER POLYMERISATION AV OLEFINER |
| FI86867C (en) | 1990-12-28 | 1992-10-26 | Neste Oy | FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN |
| FI88048C (en) | 1991-05-09 | 1993-03-25 | Neste Oy | Coarse-grained polyolefin, its method of preparation and a catalyst used in the method |
| FI88047C (en) | 1991-05-09 | 1993-03-25 | Neste Oy | Catalyst-based catalyst for polymerization of olivines |
| US5416228A (en) | 1991-10-07 | 1995-05-16 | Fina Technology, Inc. | Process and catalyst for producing isotactic polyolefins |
| IT1260495B (en) | 1992-05-29 | 1996-04-09 | Himont Inc | CONCENTRATES SUITABLE FOR THE PREPARATION OF FUNCTIONALIZED POLYOLEFINS AND FUNCTIONALIZATION PROCESS THROUGH THOSE CONCENTRATES |
| AT403376B (en) | 1995-07-03 | 1998-01-26 | Danubia Petrochem Polymere | METALLOCENES WITH SILYL-SUBSTITUTED BRIDGES AND THEIR USE FOR OLEFIN POLYMERIZATION |
| FI104826B (en) | 1996-01-30 | 2000-04-14 | Borealis As | Heteroatom-substituted metallose compounds for catalytic systems in olefin polymerization and process for their preparation |
| FI971565A (en) | 1997-04-14 | 1998-10-15 | Borealis As | Substituted metallocene compounds for catalyst systems intended for polymerization of olefins, intermediates and processes for their preparation |
| GB9708487D0 (en) | 1997-04-25 | 1997-06-18 | Bp Chem Int Ltd | Novel catalysts for olefin polymerisation |
| US6316562B1 (en) | 1997-06-10 | 2001-11-13 | Peroxid-Chemie Gmbh & Co. Kg | Catalyst systems for (co-)polymerization reactions, metallocene amide halogenides, the production and use thereof |
| FI111848B (en) | 1997-06-24 | 2003-09-30 | Borealis Tech Oy | Process and equipment for the preparation of homopolymers and copolymers of propylene |
| KR100516336B1 (en) | 1997-09-05 | 2005-09-22 | 비피 케미칼즈 리미티드 | Polymerisation catalysts |
| GB9721559D0 (en) | 1997-10-11 | 1997-12-10 | Bp Chem Int Ltd | Novel polymerisation catalysts |
| FI980342A0 (en) | 1997-11-07 | 1998-02-13 | Borealis As | Polymerroer och -roerkopplingar |
| FI974175A (en) | 1997-11-07 | 1999-05-08 | Borealis As | Process for producing polypropylene |
| US6875721B1 (en) | 1997-12-23 | 2005-04-05 | Borealis Technology Oy | Soluble magnesium dihalide complex, preparation and use |
| GB9826874D0 (en) | 1998-12-07 | 1999-01-27 | Borealis As | Process |
| FI990003A (en) | 1999-01-04 | 2000-07-05 | Borealis Polymers Oy | Polymer composition, process for the preparation thereof and films made therefrom |
| FI991057A0 (en) | 1999-05-07 | 1999-05-07 | Borealis As | High stiffness propylene polymers and process for their preparation |
| DE60221966T2 (en) | 2002-04-24 | 2007-12-20 | Borealis Polyolefine Gmbh | polypropylene compositions |
| AU2002323878A1 (en) | 2002-06-25 | 2004-01-06 | Borealis Technology Oy | Polyolefin with improved scratch resistance and process for producing the same |
| US8003725B2 (en) * | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
| EP1484343A1 (en) | 2003-06-06 | 2004-12-08 | Universiteit Twente | Process for the catalytic polymerization of olefins, a reactor system and its use in the same process |
| EP1741725B1 (en) | 2005-07-08 | 2014-04-09 | Borealis Technology Oy | Propylene polymer composition |
| EP1935938A1 (en) * | 2006-12-18 | 2008-06-25 | Borealis Technology Oy | Improved high melt flow heterophasic polypropylene copolymers |
| EP2092015B1 (en) | 2006-12-20 | 2012-11-14 | Basell Poliolefine Italia S.r.l. | Filled polyolefin compositions |
| WO2008074712A1 (en) | 2006-12-20 | 2008-06-26 | Basell Poliolefine Italia S.R.L. | Polypropylene compositions containing fillers and/or pigments |
| EP2062936A1 (en) | 2007-11-20 | 2009-05-27 | Borealis Technology OY | Improved glass fiber reinforced polypropylene |
-
2009
- 2009-10-09 ES ES09172622T patent/ES2385459T3/en active Active
- 2009-10-09 PL PL09172622T patent/PL2308923T3/en unknown
- 2009-10-09 EP EP09172622A patent/EP2308923B1/en active Active
- 2009-10-09 SI SI200930273T patent/SI2308923T1/en unknown
-
2010
- 2010-10-01 KR KR1020127011573A patent/KR101411691B1/en not_active IP Right Cessation
- 2010-10-01 CN CN201080044441.1A patent/CN102575073B/en not_active Expired - Fee Related
- 2010-10-01 AU AU2010305546A patent/AU2010305546B2/en not_active Ceased
- 2010-10-01 BR BR112012007696-5A patent/BR112012007696B1/en active IP Right Grant
- 2010-10-01 US US13/499,992 patent/US9382410B2/en active Active
- 2010-10-01 WO PCT/EP2010/064640 patent/WO2011042364A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435313A (en) * | 2002-01-30 | 2003-08-13 | 玛志达株式会社 | Glass filament reinforced resin material for shaping, resin shaped article shaping method and said resin shaped article |
Also Published As
| Publication number | Publication date |
|---|---|
| PL2308923T3 (en) | 2012-11-30 |
| AU2010305546B2 (en) | 2013-05-09 |
| BR112012007696A2 (en) | 2020-08-11 |
| KR20120062021A (en) | 2012-06-13 |
| US20120225993A1 (en) | 2012-09-06 |
| KR101411691B1 (en) | 2014-06-25 |
| EP2308923A1 (en) | 2011-04-13 |
| US9382410B2 (en) | 2016-07-05 |
| BR112012007696B1 (en) | 2021-11-03 |
| ES2385459T3 (en) | 2012-07-25 |
| CN102575073A (en) | 2012-07-11 |
| WO2011042364A1 (en) | 2011-04-14 |
| AU2010305546A1 (en) | 2012-05-31 |
| EP2308923B1 (en) | 2012-05-16 |
| SI2308923T1 (en) | 2012-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102575073B (en) | Glass fibre composite of improved processability | |
| US10059785B2 (en) | Polypropylene-polyethylene composition with improved flowability | |
| US9650504B2 (en) | High-flow fiber reinforced polypropylene composition | |
| CN103814078B (en) | Forming composition | |
| EP1753813B1 (en) | Polyolefin composition having a high balance of stiffness, impact strength and elongation at break and low thermal shrinkage | |
| US20170044359A1 (en) | Polypropylene - polyethylene blends with improved properties | |
| CN102066478A (en) | Thermoplastic polyolefins with high flowability and excellent surface quality produced by a multistage process | |
| CN103080212A (en) | Stiff polypropylene composition with excellent elongation at break | |
| CA2989492C (en) | Fiber reinforced polypropylene composition with high strain at break | |
| CN109804016A (en) | Fiber reinforced polypropylene composite material | |
| JP5032980B2 (en) | Polyolefin masterbatch and composition suitable for injection molding | |
| KR101992592B1 (en) | Fiber reinforced polypropylene composite | |
| KR20070018922A (en) | Polyolefin masterbatch and composition suitable for injection molding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140319 Termination date: 20181001 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |